Sample records for eutectics moas cras

As in a recent study for MnAs a two centre tight binding model consisting of itinerant metal d-states hybridizing with non-metal p-states was applied for CrAs and FeAs to calculate unpolarized and spin polarized local densities of states, ferromagnetic moments and band energies. The factor for the change of the d-band width relative to MnAs was estimated to be 1.3 for CrAs and 0.8 for FeAs. The self-consistent separation of the p- and d-band centres amounts to -1.3 eV for CrAs and -0.5 eV for FeAs providing a charge transfer of 0.8 and 0.6 electrons from the metal to the As atoms, correspondingly. One B8 1 structure and two B31 structures according to low and high temperature phases were studied for each compound. For CrAs self-consistent magnetic moments of 1.58 and 1.2μ B were obtained, respectively. For FeAs no ferromagnetic moment could be stabilized unless the d-band width was substantially reduced. The results are discussed with respect to MnAs. The model is able to reproduce the increase and breakdown of the magnetic moment for the series CrAs-MnAs-FeAs. Furthermore, the correct structural trend B31-B8 1-B31 is obtained if the band energy differences are corrected by a constant of 0.3 eV. This correction is attributed to the failure of the model to provide absolute differences of total energies.

CrAs was observed to possess the bulk superconductivity under high-pressure conditions. To understand the superconducting mechanism and explore the correlation between the structure and superconductivity, the high-pressure structural evolution of CrAs was investigated using the angle-dispersive X-ray diffraction (XRD) method. The structure of CrAs remains stable up to 1.8 GPa, whereas the lattice parameters exhibit anomalous compression behaviors. With increasing pressure, the lattice parameters a and c both demonstrate a nonmonotonic change, and the lattice parameter b undergoes a rapid contraction at ∼0.18−0.35 GPa, which suggests that a pressure-induced isostructural phase transition occurs in CrAs. Above the phase transition pressure, the axial compressibilities of CrAs present remarkable anisotropy. A schematic band model was used to address the anomalous compression behavior of CrAs. The present results shed light on the structural and related electronic responses to high pressure, which play a key role toward understanding the superconductivity of CrAs. PMID:26627230

The Mission Operations Assurance (MOA) discipline actively participates as a project member to achieve their common objective of full mission success while also providing an independent risk assessment to the Project Manager. The cornerstone element of MOA is the independent assessment of the risks the project faces in executing its mission. Especially as the project approaches critical mission events, it becomes imperative to clearly identify and assess the risks the project faces. This has been the paradigm for robotic space exploration missions, but does the same apply to commercial space operations? This is the question which is the driver for this year's MOA track at the 18th Annual Improving Space Operations workshop in April at the Jet Propulsion Laboratory, and the question we examine in this paper. Corollaries to this driving question are why shouldn't MOA apply and are there factors beyond mission success with acceptable risk which apply to commercial space operations that are not present in government scientific missions? To address these questions, areas we focus on include risk (both mission and profit) management for commercial space operations and the practical extension of robotic mission MOA to commercial space operations. Another key area to look at is command file errors which are a major concern for deep space robotic missions, but can we worry about them less with manned missions or unmanned supply mission? Further, with the growing concern about space debris, we delve into the role of MOA relative to End-of-Mission activities. This paper examines these topics and in particular the perspectives presented at the workshop to begin charting the appropriate course for MOA in the emerging sector of Commercial Space Operations.

We report that the recent discovery of pressure (p) induced superconductivity in the binary helimagnet CrAs has raised questions on how superconductivity emerges from the magnetic state and on the mechanism of the superconducting pairing. In the present work the suppression of magnetism and the occurrence of superconductivity in CrAs were studied by means of muon spin rotation. The magnetism remains bulk up to p ≃ 3.5 kbar while its volume fraction gradually decreases with increasing pressure until it vanishes at p ≃ 7 kbar. At 3.5 kbar superconductivity abruptly appears with its maximum Tc ≃ 1.2 K which decreases upon increasing the pressure. In the intermediate pressure region (3.5≲ p ≲ 7 kbar) the superconducting and the magnetic volume fractions are spatially phase separated and compete for phase volume. Our results indicate that the less conductive magnetic phase provides additional carriers (doping) to the superconducting parts of the CrAs sample thus leading to an increase of the transition temperature (Tc) and of the superfluid density (ρs). A scaling of ρs with Tc3.2 as well as the phase separation between magnetism and superconductivity point to a conventional mechanism of the Cooper-pairing in CrAs.

The recent discovery of pressure (p) induced superconductivity in the binary helimagnet CrAs has raised questions on how superconductivity emerges from the magnetic state and on the mechanism of the superconducting pairing. In the present work the suppression of magnetism and the occurrence of superconductivity in CrAs were studied by means of muon spin rotation. The magnetism remains bulk up to p ≃ 3.5 kbar while its volume fraction gradually decreases with increasing pressure until it vanishes at p ≃ 7 kbar. At 3.5 kbar superconductivity abruptly appears with its maximum Tc ≃ 1.2 K which decreases upon increasing the pressure. In the intermediate pressure region (3.5 < or ~ p < or ~ 7 kbar) the superconducting and the magnetic volume fractions are spatially phase separated and compete for phase volume. Our results indicate that the less conductive magnetic phase provides additional carriers (doping) to the superconducting parts of the CrAs sample thus leading to an increase of the transition temperature (Tc) and of the superfluid density (ρs). A scaling of ρs with Tc(3.2) as well as the phase separation between magnetism and superconductivity point to a conventional mechanism of the Cooper-pairing in CrAs. PMID:26346548

The recent discovery of pressure (p) induced superconductivity in the binary helimagnet CrAs has raised questions on how superconductivity emerges from the magnetic state and on the mechanism of the superconducting pairing. In the present work the suppression of magnetism and the occurrence of superconductivity in CrAs were studied by means of muon spin rotation. The magnetism remains bulk up to p 3.5 kbar while its volume fraction gradually decreases with increasing pressure until it vanishes at p 7 kbar. At 3.5 kbar superconductivity abruptly appears with its maximum Tc 1.2 K which decreases upon increasing the pressure. In the intermediate pressure region (3.5 p 7 kbar) the superconducting and the magnetic volume fractions are spatially phase separated and compete for phase volume. Our results indicate that the less conductive magnetic phase provides additional carriers (doping) to the superconducting parts of the CrAs sample thus leading to an increase of the transition temperature (Tc) and of the superfluid density (ρs). A scaling of ρs with as well as the phase separation between magnetism and superconductivity point to a conventional mechanism of the Cooper-pairing in CrAs. PMID:26346548

We report a systematically study of resistivity and specific heat on phosphorus doped CrAs1-xPx single crystals with x =0 to 0.2. With the increasing of phosphorus doping concentration x, the magnetic and structural transition temperature TN is suppressed. Non-fermi liquid behavior and quantum criticality phenomenon are observed from low temperature resistivity around critical doping with xc ~0.05 where the long-range antiferromagnetic ordering is completely suppressed. The low temperature specific heat of CrAs1-xPx is contributed by the thermal excitation of phonons and electrons. The electronic specific heat coefficient γ, which reflects the effective mass of quasi-particles, shows maximum around xc ~0.05, also indicating the existence of quantum critical phenomenon around the critical doping. The value of Kadowaki-Woods ratio of CrAs1-xPx shows no significant different from that of CrAs. Work is done in collaboration with Fukun Lin, Wei Wu, Ping Zheng, Guozhi Fan, Jinguang Cheng.

The objectives of this program are to determine the influence of convection on the microstructure of eutectics and to develop a technique for revealing the longitudinal microstructure of the MnBi-Bi eutectic. Both objectives aim at trying to explain the observed influence of space processing on the microstructure of MnBi-Bi. A computer program was developed and used to determine the concentration field in front of a growing lamellar eutectic. From this the deviation of the interfacial concentration from the eutectic composition was calculated as a function of eutectic composition, freezing rate, convection, and lamellar spacing.

CrAs is an antiferromagnetic metal, which shows a helical spin structure accompanied by an abrupt lattice expansion at TN ~260 K in ambient pressure. With applying pressure, the magnetic transition is suppressed and superconductivity appears with a maximum transition temperature of ~2 K. Since Cr has the spin degree of freedom, elucidating the magnetic contribution to the superconductivity is crucial to understand the pairing mechanism. However, inelastic neutron scattering (INS) measurement under high pressure is challenging due to sample space limitation. Therefore, we studied chemical pressure effect by substituting As by P, which is found to be almost the same as the external pressure. We performed INS experiments in undoped and P-doped CrAs using powder samples. The results in the P-doped CrAs clearly indicate that the antiferromagnetic fluctuations still remain above the critical P content, where the long range magnetic order is suppressed, suggesting a coupling between the magnetism and the superconductivity. This research at ORNL's High Flux Isotope Reactor and Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy.

We report that the recent discovery of pressure (p) induced superconductivity in the binary helimagnet CrAs has raised questions on how superconductivity emerges from the magnetic state and on the mechanism of the superconducting pairing. In the present work the suppression of magnetism and the occurrence of superconductivity in CrAs were studied by means of muon spin rotation. The magnetism remains bulk up to p ≃ 3.5 kbar while its volume fraction gradually decreases with increasing pressure until it vanishes at p ≃ 7 kbar. At 3.5 kbar superconductivity abruptly appears with its maximum Tc ≃ 1.2 K which decreasesmore » upon increasing the pressure. In the intermediate pressure region (3.5≲ p ≲ 7 kbar) the superconducting and the magnetic volume fractions are spatially phase separated and compete for phase volume. Our results indicate that the less conductive magnetic phase provides additional carriers (doping) to the superconducting parts of the CrAs sample thus leading to an increase of the transition temperature (Tc) and of the superfluid density (ρs). A scaling of ρs with Tc3.2 as well as the phase separation between magnetism and superconductivity point to a conventional mechanism of the Cooper-pairing in CrAs.« less

... eliminate administrative duplication, when such duplication does not contribute to the overall decision-making process. MOAs for purposes of this regulation will not be used to implement provisions not...

The suppression of magnetic order with pressure concomitant with the appearance of pressure-induced superconductivity was recently discovered in CrAs. Here we present a neutron diffraction study of the pressure evolution of the helimagnetic ground-state towards and in the vicinity of the superconducting phase. Neutron diffraction on polycrystalline CrAs was employed from zero pressure to 0.65 GPa and at various temperatures. The helimagnetic long-range order is sustained under pressure and the magnetic propagation vector does not show any considerable change. The average ordered magnetic moment is reduced from 1.73(2) μB at ambient pressure to 0.4(1) μB close to the critical pressuremore » Pc ≈ 0.7 GPa, at which magnetic order is completely suppressed. The width of the magnetic Bragg peaks strongly depends on temperature and pressure, showing a maximum in the region of the onset of superconductivity. In conclusion, we interpret this as associated with competing ground-states in the vicinity of the superconducting phase.« less

The suppression of magnetic order with pressure concomitant with the appearance of pressure-induced superconductivity was recently discovered in CrAs. Here we present a neutron diffraction study of the pressure evolution of the helimagnetic ground-state towards and in the vicinity of the superconducting phase. Neutron diffraction on polycrystalline CrAs was employed from zero pressure to 0.65 GPa and at various temperatures. The helimagnetic long-range order is sustained under pressure and the magnetic propagation vector does not show any considerable change. The average ordered magnetic moment is reduced from 1.73(2) μB at ambient pressure to 0.4(1) μB close to the critical pressure Pc ≈ 0.7 GPa, at which magnetic order is completely suppressed. The width of the magnetic Bragg peaks strongly depends on temperature and pressure, showing a maximum in the region of the onset of superconductivity. In conclusion, we interpret this as associated with competing ground-states in the vicinity of the superconducting phase.

WE PERFORM THE FIRST MULTIDISCIPLINARY STUDY OF PARASITES FROM AN EXTINCT MEGAFAUNAL CLADE USING COPROLITES FROM THE NEW ZEALAND MOA (AVES: Dinornithiformes). Ancient DNA and microscopic analyses of 84 coprolites deposited by four moa species (South Island giant moa, Dinornis robustus; little bush moa, Anomalopteryx didiformis; heavy-footed moa, Pachyornis elephantopus; and upland moa, Megalapteryx didinus) reveal an array of gastrointestinal parasites including coccidians (Cryptosporidium and members of the suborder Eimeriorina), nematodes (Heterakoidea, Trichostrongylidae, Trichinellidae) and a trematode (Echinostomida). Parasite eggs were most prevalent and diverse in coprolites from lowland sites, where multiple sympatric moa species occurred and host density was therefore probably higher. Morphological and phylogenetic evidence supports a possible vicariant Gondwanan origin for some of the moa parasites. The discovery of apparently host-specific parasite taxa suggests paleoparasitological studies of megafauna coprolites may provide useful case-studies of coextinction. PMID:23451203

We perform the first multidisciplinary study of parasites from an extinct megafaunal clade using coprolites from the New Zealand moa (Aves: Dinornithiformes). Ancient DNA and microscopic analyses of 84 coprolites deposited by four moa species (South Island giant moa, Dinornis robustus; little bush moa, Anomalopteryx didiformis; heavy-footed moa, Pachyornis elephantopus; and upland moa, Megalapteryx didinus) reveal an array of gastrointestinal parasites including coccidians (Cryptosporidium and members of the suborder Eimeriorina), nematodes (Heterakoidea, Trichostrongylidae, Trichinellidae) and a trematode (Echinostomida). Parasite eggs were most prevalent and diverse in coprolites from lowland sites, where multiple sympatric moa species occurred and host density was therefore probably higher. Morphological and phylogenetic evidence supports a possible vicariant Gondwanan origin for some of the moa parasites. The discovery of apparently host-specific parasite taxa suggests paleoparasitological studies of megafauna coprolites may provide useful case-studies of coextinction. PMID:23451203

The antiferromagnetic NiAs-type compound CrAs0.3Sb0.7 exhibits a spin-reorientation transition at Tt=140 K which is accompanied by a large discontinuous change of the lattice parameters and a thermal hysteresis of 20 K, while no magnetic hysteresis is observed. Around Tt, an inverse magnetocaloric effect with a maximum magnetic-entropy change of 0.2 J/kg K at a field change from 0to 7 T is observed. After several thermo-cycles, a large irreversible lattice expansion of the c axis of 0.44% occurs. The irreversible lattice expansion may induce micro-cracks and leads to a sharp increase of the resistivity close to Tt in the cooling process and to a shift of the resistivity curve, ρ(T), to higher values with increasing number of warming and cooling cycles.

The modifications that occur on proteins in natural environments over time are not well studied, yet characterizing them is vital to correctly interpret sequence data recovered from fossils. The recently extinct moa (Dinornithidae) is an excellent candidate for investigating the preservation of proteins, their post-translational modifications (PTMs) and diagenetic alterations during degradation. Moa protein extracts were analysed using mass spectrometry, and peptides from collagen I, collagen II and collagen V were identified. We also identified biologically derived PTMs (i.e. methylation, di-methylation, alkylation, hydroxylation, fucosylation) on amino acids at locations consistent with extant proteins. In addition to these in vivo modifications, we detected novel modifications that are probably diagenetically derived. These include loss of hydroxylation/glutamic semialdehyde, carboxymethyllysine and peptide backbone cleavage, as well as previously noted deamidation. Moa collagen sequences and modifications provide a baseline by which to evaluate proteomic studies of other fossils, and a framework for defining the molecular relationship of moa to other closely related taxa. PMID:25972464

The modifications that occur on proteins in natural environments over time are not well studied, yet characterizing them is vital to correctly interpret sequence data recovered from fossils. The recently extinct moa (Dinornithidae) is an excellent candidate for investigating the preservation of proteins, their post-translational modifications (PTMs) and diagenetic alterations during degradation. Moa protein extracts were analysed using mass spectrometry, and peptides from collagen I, collagen II and collagen V were identified. We also identified biologically derived PTMs (i.e. methylation, di-methylation, alkylation, hydroxylation, fucosylation) on amino acids at locations consistent with extant proteins. In addition to these in vivo modifications, we detected novel modifications that are probably diagenetically derived. These include loss of hydroxylation/glutamic semialdehyde, carboxymethyllysine and peptide backbone cleavage, as well as previously noted deamidation. Moa collagen sequences and modifications provide a baseline by which to evaluate proteomic studies of other fossils, and a framework for defining the molecular relationship of moa to other closely related taxa. PMID:25972464

Pressure-induced superconductivity was recently discovered in the binary helimagnet CrAs. We report the results of measurements of nuclear quadrupole resonance for CrAs under pressure. In the vicinity of the critical pressure P(c) between the helimagnetic (HM) and paramagnetic (PM) phases, a phase separation is observed. The large internal field remaining in the phase-separated HM state indicates that the HM phase disappears through a strong first-order transition. This indicates the absence of a quantum critical point in CrAs; however, the nuclear spin-lattice relaxation rate 1/T(1) reveals that substantial magnetic fluctuations are present in the PM state. The absence of a coherence effect in 1/T(1) in the superconducting state provides evidence that CrAs is the first Cr-based unconventional superconductor. PMID:25839303

A theory was developed for the influence of convection on the microstructure of lamellar eutectics. Convection is predicted to produce a coarser microstructure, especially at low freezing rates and large volume fractions of the minority phase. Similary convection is predicted to lower the interfacial undercooling, especially at low freezing rates. Experiments using spin-up/spin-down were performed on the Mn-Bi eutectic. This stirring had a dramatic effect on the microstructure, not only making it coarser but at low freezing rates also changing the morphology of the MnBi. The coarsering persisted to moderately high freezing rates. At the lowest freezing rate, vigorous stirring caused the MnBi to be concentrated at the periphery of the ingot and absent along the center. Progress was made on developing a technique for revealing the three-dimensional microstructure of the MnBi eutectic by time-lapse videotaping while etching.

The discovery in New Zealand of Late Holocene deposits of coprolites from extinct avian megaherbivores has provided a unique opportunity to gain a detailed insight into the ecology of these birds across ecologically diverse habitats. Macrofossil analysis of 116 coprolites of the giant ratite moa (Aves, Dinornithiformes) reveals a diverse diet of herbs and low shrubs in both semi-arid and high rainfall ecological zones, overturning previous models of moa as dominantly browsers of trees and shrubs. Ancient DNA analysis identified coprolites from four moa species (South Island giant moa, Dinornis robustus; upland moa, Megalapteryx didinus; heavy-footed moa, Pachyornis elephantopus and stout-legged moa, Euryapteryx gravis), revealing a larger dietary variation between habitat types than between species. The new data confirm that moa fed on a variety of endemic plant taxa with unusual growth forms previously suggested to have co-evolved with moa. Lastly, the feeding ecologies of moa are shown to be widely different to introduced mammalian herbivores.

Transition-metal oxides or pnictides are in rich of novel and intriguing electronic behaviors due to multiple quantum orders and competing phenomena. Among the different electronic states, the emergence of superconductivity in the vicinity of other quantum orders is at the heart of the rich physics. Superconductivity has been observed in a majority of 3d transition-metal compounds except for the Cr- and Mn- based compounds. It is thus of high interest in exploring possible superconductivity in those systems. In this talk, I will present the discovery of superconductivity on the verge of antiferromagnetic order in CrAs via the application of external high pressure. Bulk superconductivity with Tc ~ 2 K emerges at the critical pressure Pc ~ 8 kbar, where the first-order antiferromagnetic transition at TN ~ 265 K under ambient pressure is completely suppressed. In addition, quantum criticality and non-Fermi liquid behavior are observed near Pc, which we interpret as originating from a nearly second-order magnetic quantum phase transition that is concomitant with a first-order structural transition. The present finding opens a new avenue for searching novel superconductors in the Cr and other 3d transitional-metal based systems. In collaboration with Wei Wu, Jinguang Cheng, Kazuyuki Matsubayashi, Panpan Kong, Fukun Lin, Changqing Jin, Nanlin Wang, Yoshiya Uwatoko, Rong Yi, and Qimiao Si.

Experimental data are given for BiMn/Bi rod eutectic and Fe3C/Fe lamellar eutectic solidified in low gravity. Eutectic spacing is summarized for various alloy systems solidified in low gravity. On-eutectic and off-eutectic models are evaluated with respect to the low-gravity solidification data. The models examined are inadequate for quantitative prediction of phase spacing for on-eutectic solidification in low gravity.

The moa (Aves: Dinornithiformes) of New Zealand represent one of the extinct iconic taxa that define the field of ancient DNA (aDNA), and after almost two decades of genetic scrutiny of bones, feathers, coprolites, mummified tissue, eggshell, and sediments, our knowledge of these prehistoric giants has increased significantly. Thanks to molecular and morphological-based research, the insights that have been obtained into moa phylogenetics, phylogeography, and palaeobiology exceeds that of any other extinct taxon. This review documents the strengths of applying a multidisciplinary approach when studying extinct taxa but also shows that cross-disciplinary controversies still remain at the most fundamental levels, with highly conflicting interpretations derived from aDNA and morphology. Moa species diversity, for example, is still heavily debated, as well as their relationship with other ratites and the mode of radiation. In addition to increasing our knowledge on a lineage of extinct birds, further insights into these aspects can clarify some of the basal splits in avian evolution, and the evolutionary implications of the breakup of the prehistoric supercontinent Gondwana. Did a flightless moa ancestor drift away on proto New Zealand (Moa's Ark) or did a volant ancestor arrive by flight? Here we provide an overview of 19 years of aDNA research on moa, critically assess the attempts and controversies in placing the moa lineage among palaeognath birds, and discuss the factors that facilitated the extensive radiation of moa. Finally, we identify the most obvious gaps in the current knowledge to address the future potential research areas in moa genetics. PMID:21596537

The Galactic bulge source MOA-2010-BLG-523S exhibited short-term deviations from a standard microlensing light curve near the peak of an A {sub max} {approx} 265 high-magnification microlensing event. The deviations originally seemed consistent with expectations for a planetary companion to the principal lens. We combine long-term photometric monitoring with a previously published high-resolution spectrum taken near peak to demonstrate that this is an RS CVn variable, so that planetary microlensing is not required to explain the light-curve deviations. This is the first spectroscopically confirmed RS CVn star discovered in the Galactic bulge.

More than 60 years after the later Nobel laureate Hannes Alfvén had published a letter stating that oscillating magnetic fields can accelerate ionised matter via magneto-hydrodynamic interactions in a wave like fashion, the technical implementation of Alfvén waves for propulsive purposes has been proposed, patented and examined for the first time by a group of inventors. The name of the concept, utilising Alfvén waves to accelerate ionised matter for propulsive purposes, is MOA-magnetic field oscillating amplified thruster. Alfvén waves are generated by making use of two coils, one being permanently powered and serving also as magnetic nozzle, the other one being switched on and off in a cyclic way, deforming the field lines of the overall system. It is this deformation that generates Alfvén waves, which are in the next step used to transport and compress the propulsive medium, in theory leading to a propulsion system with a much higher performance than any other electric propulsion system. Based on computer simulations, which were conducted to get a first estimate on the performance of the system, MOA is a corrosion free and highly flexible propulsion system, whose performance parameters might easily be adapted in flight, by changing the mass flow and/or the power level. As such the system is capable to deliver a maximum specific impulse of 13 116 s (12.87 mN) at a power level of 11.16 kW, using Xe as propellant, but can also be attuned to provide a thrust of 236.5 mN (2411 s) at 6.15 kW of power. First tests-that are further described in this paper-have been conducted successfully and underline the feasibility of the concept. While space propulsion is expected to be the prime application for MOA and is supported by numerous applications such as Solar and/or Nuclear Electric Propulsion or even as an "afterburner system" for nuclear thermal propulsion, other terrestrial applications can be thought of as well, making the system highly suited for a common space

Coatings developed to provide oxidation protection for the directionally-solidified eutectic alloy NiTaC-B (4.4 weight percent Cr) were evaluated. Of seven Co-, Fe- and Ni-base coatings that were initially investigated, best resistance to cyclic oxidation was demonstrated by duplex coatings fabricated by depositing a layer of NiCrAl(Y) by vacuum evaporation from an electron beam source followed by deposition of an Al overlayer using the pack cementation process. It was found that addition of carbon to the coating alloy substantially eliminated the problem of fiber denudation in TaC-type eutectic alloys. Burner rig cycled NiTaC-B samples coated with Ni-20Cr-5Al-0.1C-0.1Y+Al and rupture-tested at 1100 deg C performed as well as or better than uncoated, vacuum cycled and air-tested NiTaC-13; however, a slight degradation with respect to uncoated material was noted in air-stress rupture tests at 870 deg C for both cycled and uncycled samples.

The present paper addresses the long-standing composition puzzle of eutectic points by introducing a new structural tool for the description of short-range-order structural unit, the cluster-plus-glue-atom model. In this model, any structure is dissociated into a 1st-neighbor cluster and a few glue atoms between the clusters, expressed by a cluster formula [cluster]gluex. This model is applied here to establish the structural model for eutectic liquids, assuming that a eutectic liquid consist of two subunits issued from the relevant eutectic phases, each being expressed by the cluster formula for ideal metallic glasses, i.e., [cluster](glue atom)1 or 3. A structural unit is then composed of two clusters from the relevant eutectic phases plus 2, 4, or 6 glue atoms. Such a dual cluster formulism is well validated in all boron-containing (except those located by the extreme phase diagram ends) and in some commonly-encountered binary eutectics, within accuracies below 1 at.%. The dual cluster formulas vary extensively and are rarely identical even for eutectics of close compositions. They are generally formed with two distinctly different cluster types, with special cluster matching rules such as cuboctahedron plus capped trigonal prism and rhombidodecahedron plus octahedral antiprism.

The present paper addresses the long-standing composition puzzle of eutectic points by introducing a new structural tool for the description of short-range-order structural unit, the cluster-plus-glue-atom model. In this model, any structure is dissociated into a 1(st)-neighbor cluster and a few glue atoms between the clusters, expressed by a cluster formula [cluster]gluex. This model is applied here to establish the structural model for eutectic liquids, assuming that a eutectic liquid consist of two subunits issued from the relevant eutectic phases, each being expressed by the cluster formula for ideal metallic glasses, i.e., [cluster](glue atom)(1 or 3). A structural unit is then composed of two clusters from the relevant eutectic phases plus 2, 4, or 6 glue atoms. Such a dual cluster formulism is well validated in all boron-containing (except those located by the extreme phase diagram ends) and in some commonly-encountered binary eutectics, within accuracies below 1 at.%. The dual cluster formulas vary extensively and are rarely identical even for eutectics of close compositions. They are generally formed with two distinctly different cluster types, with special cluster matching rules such as cuboctahedron plus capped trigonal prism and rhombidodecahedron plus octahedral antiprism. PMID:26658618

The present paper addresses the long-standing composition puzzle of eutectic points by introducing a new structural tool for the description of short-range-order structural unit, the cluster-plus-glue-atom model. In this model, any structure is dissociated into a 1st-neighbor cluster and a few glue atoms between the clusters, expressed by a cluster formula [cluster]gluex. This model is applied here to establish the structural model for eutectic liquids, assuming that a eutectic liquid consist of two subunits issued from the relevant eutectic phases, each being expressed by the cluster formula for ideal metallic glasses, i.e., [cluster](glue atom)1 or 3. A structural unit is then composed of two clusters from the relevant eutectic phases plus 2, 4, or 6 glue atoms. Such a dual cluster formulism is well validated in all boron-containing (except those located by the extreme phase diagram ends) and in some commonly-encountered binary eutectics, within accuracies below 1 at.%. The dual cluster formulas vary extensively and are rarely identical even for eutectics of close compositions. They are generally formed with two distinctly different cluster types, with special cluster matching rules such as cuboctahedron plus capped trigonal prism and rhombidodecahedron plus octahedral antiprism. PMID:26658618

The effect of gravity on eutectic solidification was investigated experimentally for Pb-Sn binary eutectic alloys. It is found that the separation of the primary crystals of the binary system from the coupled eutectic occurs over a wide range of cooling rates and gravitational fields (100-100,000 g). The separation is strongly influenced by the nucleation behavior of the particular alloy system. A mechanism for the strong phase separation is postulated on the basis of cloud convection models in atmospheric convection.

Knowledge of extinct herbivore community structuring is essential for assessing the wider ecological impacts of Quaternary extinctions and determining appropriate taxon substitutes for rewilding. Here, we demonstrate the potential for coprolite studies to progress beyond single-species diet reconstructions to resolving community-level detail. The moa (Aves: Dinornithiformes) of New Zealand are an intensively studied group of nine extinct herbivore species, yet many details of their diets and community structuring remain unresolved. We provide unique insights into these aspects of moa biology through analyses of a multispecies coprolite assemblage from a rock overhang in a montane river valley in southern New Zealand. Using ancient DNA (aDNA), we identified 51 coprolites, which included specimens from four sympatric moa species. Pollen, plant macrofossils, and plant aDNA from the coprolites chronicle the diets and habitat preferences of these large avian herbivores during the 400 y before their extinction (∼1450 AD). We use the coprolite data to develop a paleoecological niche model in which moa species were partitioned based on both habitat (forest and valley-floor herbfield) and dietary preferences, the latter reflecting allometric relationships between body size, digestive efficiency, and nutritional requirements. Broad ecological niches occupied by South Island giant moa (Dinornis robustus) and upland moa (Megalapteryx didinus) may reflect sexual segregation and seasonal variation in habitat use, respectively. Our results show that moa lack extant ecological analogs, and their extinction represents an irreplaceable loss of function from New Zealand’s terrestrial ecosystems. PMID:24082104

Knowledge of extinct herbivore community structuring is essential for assessing the wider ecological impacts of Quaternary extinctions and determining appropriate taxon substitutes for rewilding. Here, we demonstrate the potential for coprolite studies to progress beyond single-species diet reconstructions to resolving community-level detail. The moa (Aves: Dinornithiformes) of New Zealand are an intensively studied group of nine extinct herbivore species, yet many details of their diets and community structuring remain unresolved. We provide unique insights into these aspects of moa biology through analyses of a multispecies coprolite assemblage from a rock overhang in a montane river valley in southern New Zealand. Using ancient DNA (aDNA), we identified 51 coprolites, which included specimens from four sympatric moa species. Pollen, plant macrofossils, and plant aDNA from the coprolites chronicle the diets and habitat preferences of these large avian herbivores during the 400 y before their extinction (∼1450 AD). We use the coprolite data to develop a paleoecological niche model in which moa species were partitioned based on both habitat (forest and valley-floor herbfield) and dietary preferences, the latter reflecting allometric relationships between body size, digestive efficiency, and nutritional requirements. Broad ecological niches occupied by South Island giant moa (Dinornis robustus) and upland moa (Megalapteryx didinus) may reflect sexual segregation and seasonal variation in habitat use, respectively. Our results show that moa lack extant ecological analogs, and their extinction represents an irreplaceable loss of function from New Zealand's terrestrial ecosystems. PMID:24082104

Significant advances have been made in the development of an environmentally stable coating for a very high strength, directionally solidified eutectic alloy designated NiTaC-13. Three duplex (two-layer) coatings survived 3,000 hours on a cyclic oxidation test (1,100 C to 90 C). These coatings were fabricated by first depositing a layer of NiCrAl(Y) by vacuum evaporation from an electron beam heated source, followed by depositing an aluminizing overlayer. The alloy after exposure with these coatings was denuded of carbide fibers at the substrate/coating interface. It was demonstrated that TaC fiber denudation can be greatly retarded by applying a carbon-bearing coating. The coating was applied by thermal spraying followed by aluminization. Specimens coated with NiCrAlCY+Al survived over 2,000 hours in the cyclic oxidation test with essentially no TaC denudation. Coating ductility was studied for coated and heat-treated bars, and stress rupture life at 871 C and 1,100 C was determined for coated and cycled bars.

This is a presentation on some of the possible subjective decision points in a mode-of-action (MOA) analysis that incorporates some systematic review principles, using examples from the draft formaldehyde assessment to illustrate possible decisions and documentation.

New Zealand moa (Aves: Dinornithiformes) are the only late Quaternary megafauna whose extinction was clearly caused by humans. New Zealand offers the best opportunity to estimate the number of people involved in a megafaunal extinction event because, uniquely, both the Polynesian settlement of New Zealand and moa extinction are recent enough to be dated with a high degree of precision. In addition, the founding human population can be estimated from genetic evidence. Here we show that the Polynesian population of New Zealand would not have exceeded 2,000 individuals before extinction of moa populations in the habitable areas of the eastern South Island. During a brief (<150 years) period and at population densities that never exceeded ~0.01 km(-2), Polynesians exterminated viable populations of moa by hunting and removal of habitat. High human population densities are not required in models of megafaunal extinction. PMID:25378020

Two major problems associated with structural ceramics are lack of damage tolerance and insufficient strength and creep resistance at very high temperatures of interest for aerospace application. This work demonstrated that the directionally solidified eutectics can have unique poly-phase microstructures and mechanical properties superior to either constituent alone. The constraining effect of unique eutectic microstructures result in higher resistance to slow crack growth and creep. Prospect of achieving superior properties through controlled solidification are presented and this technology can also be beneficial to produce new class of materials.

We present the discovery and mass measurement of the first Neptune analog exoplanet, MOA-2013-BLG-605Lb. This planet has a mass similar to that of Neptune and it orbits at a distance of 11 times the expected position of the snow-line, which is the same position as Neptune in our Solar System. This is the first sub-Jupiter-mass exoplanet found at such a large distance from its host star, although planets at similar separations have been found by direct imaging. There are two degenerate physical solutions due to a new type of degeneracy in the microlensing parallax parameters, known as the wide degeneracy. The slightly favored model has a Neptune-mass planet orbiting a low-mass M-dwarf. The alternative model implies a mini-Neptune orbiting a brown dwarf host. The 3-D planet-host separations are 11 times or 16 times greater than the expected positions of the snow-line for these models, respectively, which are close to Neptune's separation of 11 snow-line from the Sun. This discovery suggests that Neptune-like planets orbiting at 11 snow-line are quite common, so the process that formed Uranus and Neptune in our own Solar System may be quite common in other solar systems.

Megafaunal extinction followed the prehistoric human settlement of islands across the globe, but the exact duration and dynamics of the extinction processes are difficult to determine. The New Zealand moa (Aves, Dinornithiformes) are a prime example, where, despite an extensive fossil and archaeological record, debate continues about their extinction chronology and how extinction timings varied among regions and species. We apply probabilistic sightings methods to 111 high-quality radiocarbon dates (from a pool of 653 dates) on moa remains from natural and archaeological sites to provide a high-resolution spatio-temporal chronology of moa extinction. We interpret this alongside an estimated time for the onset of hunting pressure, obtained by applying the same methods to the most reliable proxies for initial human settlement of New Zealand: coprolites of and seeds gnawed by the commensal Pacific rat (Rattus exulans). By comparing local and national extinction times, we discriminate between the point at which hunting stopped (economic extinction) and the total extinction of moa (ca 150 and 200 years after settlement, respectively). Extinction occurred contemporaneously at sites separated by hundreds of kilometres. There was little difference between the extinction times of the smallest (20-50 kg) and largest (200+ kg) moa species. Our results demonstrate how rapidly megafauna were exterminated from even large, topographically- and ecologically-diverse islands such as New Zealand, and highlight the fragility of such ecosystems in the face of human impacts.

The moa (Dinornithiformes) are large to gigantic extinct terrestrial birds of New Zealand. Knowledge about niche partitioning, feeding mode and preference among moa species is limited, hampering palaeoecological reconstruction and evaluation of the impacts of their extinction on remnant native biota, or the viability of exotic species as proposed ecological 'surrogates'. Here we apply three-dimensional finite-element analysis to compare the biomechanical performance of skulls from five of the six moa genera, and two extant ratites, to predict the range of moa feeding behaviours relative to each other and to living relatives. Mechanical performance during biting was compared using simulations of the birds clipping twigs based on muscle reconstruction of mummified moa remains. Other simulated food acquisition strategies included lateral shaking, pullback and dorsoventral movement of the skull. We found evidence for limited overlap in biomechanical performance between the extant emu (Dromaius novaehollandiae) and extinct upland moa (Megalapteryx didinus) based on similarities in mandibular stress distribution in two loading cases, but overall our findings suggest that moa species exploited their habitats in different ways, relative to both each other and extant ratites. The broad range of feeding strategies used by moa, as inferred from interspecific differences in biomechanical performance of the skull, provides insight into mechanisms that facilitated high diversities of these avian herbivores in prehistoric New Zealand. PMID:26763698

This paper presents a eutectic gold vapour laser (EGVL) which uses the eutectic alloy of gold and silicon, Au/3.15Si, as the lasant. It was observed that, at low input power operation, the presence of the silicon vapour could increase the output of the 627.8 nm laser line by (50-60)% when compared with a gold vapour laser (GVL) which uses pure gold as the lasant. The improved laser output for the EGVL may be explained by an increased electron density, as a result of Penning ionization of silicon atoms. However, for higher input power operation, the EGVL showed a slower rate of increase in its laser output power and was overtaken by GVLs at a tube operating temperature of around 1650°C. This may be explained by a lowering of the electron temperature owing to increasing inelastic collisions between the electrons and silicon atoms which, although excited, may not produce additional electrons.

New Zealand's extinct flightless moa radiated rapidly into a large number of morphologically diverse species, which produced an equally large range of egg morphologies. The exact number of moa species, as well as the characteristics of the eggs they laid, remains contentious. Moreover, like most extinct species, we understand little about their nesting and incubation habits. We used a modified ancient DNA extraction procedure to recover exogenous mitochondrial and nuclear DNA from the inside and outside surfaces of moa eggs. We used sequences from the inside of 69 eggshells to directly assign these remains to seven of the 10 currently recognized moa species. In addition we were able to assign, to the species level, six of the rare reconstructed “whole” eggs. These molecular results enabled us to identify two distinct lineages within the genus Euryapteryx. Members of these lineages differed in eggshell thickness, with one lineage being characterized by a relatively thin eggshell. Unexpectedly, several thin-shelled eggs were also shown to belong to the heaviest moa of the genera Dinornis, Euryapteryx and Emeus, making these, to our knowledge, the most fragile of all avian eggs measured to date. Moreover, sex-specific DNA recovered from the outer surfaces of eggshells belonging to species of Dinornis and Euryapteryx suggest that these very thin eggs were likely to have been incubated by the lighter males. The thin nature of the eggshells of these larger species of moa, even if incubated by the male, suggests that egg breakage in these species would have been common if the typical contact method of avian egg incubation was used. PMID:20805485

Molybdenum and tungsten cofactors share a similar pterin-based scaffold, which hosts an ene-dithiolate function being essential for the coordination of either molybdenum or tungsten. The biosynthesis of both cofactors involves a multistep pathway, which ends with the activation of the metal binding pterin (MPT) by adenylylation before the respective metal is incorporated. In the hyperthermophilic organism Pyrococcus furiosus, the hexameric protein MoaB (PfuMoaB) has been shown to catalyse MPT-adenylylation. Here we determined the crystal structure of PfuMoaB at 2.5 Å resolution and identified key residues of α3-helix mediating hexamer formation. Given that PfuMoaB homologues from mesophilic organisms form trimers, we investigated the impact on PfuMoaB hexamerization on thermal stability and activity. Using structure-guided mutagenesis, we successfully disrupted the hexamer interface in PfuMoaB. The resulting PfuMoaB-H3 variant formed monomers, dimers and trimers as determined by size exclusion chromatography. Circular dichroism spectroscopy as well as chemical cross-linking coupled to mass spectrometry confirmed a wild-type-like fold of the protomers as well as inter-subunits contacts. The melting temperature of PfuMoaB-H3 was found to be reduced by more than 15 °C as determined by differential scanning calorimetry, thus demonstrating hexamerization as key determinant for PfuMoaB thermal stability. Remarkably, while a loss of activity at temperatures higher than 50 °C was observed in the PfuMoaB-H3 variant, at lower temperatures, we determined a significantly increased catalytic activity. The latter suggests a gain in conformational flexibility caused by the disruption of the hexamerization interface. PMID:24465852

Molybdenum and tungsten cofactors share a similar pterin-based scaffold, which hosts an ene-dithiolate function being essential for the coordination of either molybdenum or tungsten. The biosynthesis of both cofactors involves a multistep pathway, which ends with the activation of the metal binding pterin (MPT) by adenylylation before the respective metal is incorporated. In the hyperthermophilic organism Pyrococcus furiosus, the hexameric protein MoaB (PfuMoaB) has been shown to catalyse MPT-adenylylation. Here we determined the crystal structure of PfuMoaB at 2.5 Å resolution and identified key residues of α3-helix mediating hexamer formation. Given that PfuMoaB homologues from mesophilic organisms form trimers, we investigated the impact on PfuMoaB hexamerization on thermal stability and activity. Using structure-guided mutagenesis, we successfully disrupted the hexamer interface in PfuMoaB. The resulting PfuMoaB-H3 variant formed monomers, dimers and trimers as determined by size exclusion chromatography. Circular dichroism spectroscopy as well as chemical cross-linking coupled to mass spectrometry confirmed a wild-type-like fold of the protomers as well as inter-subunits contacts. The melting temperature of PfuMoaB-H3 was found to be reduced by more than 15°C as determined by differential scanning calorimetry, thus demonstrating hexamerization as key determinant for PfuMoaB thermal stability. Remarkably, while a loss of activity at temperatures higher than 50°C was observed in the PfuMoaB-H3 variant, at lower temperatures, we determined a significantly increased catalytic activity. The latter suggests a gain in conformational flexibility caused by the disruption of the hexamerization interface. PMID:24465852

There are various structure-based classification schemes to categorize chemicals based on mode of action (MOA) which have been applied for both eco and human health toxicology. With increasing calls to assess thousands of chemicals, some of which have little available informatio...

On July 21, 1999, EPA and the Department of Defense (DoD) signed a Memorandum of Agreement (MOA) to collaborate on a program to test new commercial-ready environmental technologies. When private companies develop new technologies for better environmental pollution prevention, con...

... (MOA) and Improvement Plan (IP) in Connection With the Public Housing Assessment System (PHAS) AGENCY... Plan (IP). OMB Control Number: 2577-0237. Description of the need for the information and proposed use...% but not less than 60% is required to submit an Improvement Plan (IP). These plans are designed...

Background Analysis of ancient DNA has provided invaluable information on past ecologies, ancient populations, and extinct species. We used a short snippet of highly variable mitochondrial control region sequence from New Zealand’s moa to characterise a large number of bones previously intractable to DNA analysis as well as bone fragments from swamps to gain information about the haplotype diversity and phylogeography that existed in five moa species. Methodology/Principal Findings By targeting such ‘snippets’, we show that moa populations differed substantially in geographic structure that is likely to be related to population mobility and history. We show that populations of Pachyornis geranoides, Dinornis novaezealandiae, and Dinornis robustus were highly structured and some appear to have occupied the same geographic location for hundreds of thousands of years. In contrast, populations of the moa Anomalopteryx didiformis and Euryapteryx curtus were widespread, with specific populations of the latter occupying both the North and South Islands of New Zealand. We further show that for a specific area, in this case a North Island swamp, complete haplotype diversity and even sex can be recovered from collections of small, often discarded, bone fragments. Conclusions/Significance Short highly variable mitochondrial ‘snippets’ allow successful typing of environmentally damaged and fragmented skeletal material, and can provide useful information about ancient population diversity and structure without the need to sample valuable, whole bones often held by museums. PMID:23341875

It is a well known fact that CRA`s are used in the oil industry as one way to control erosion/corrosion effects. Many fields in the eastern region of Venezuela are considered corrosive due to the presence of CO{sub 2} (5 to 20%), H{sub 2}S (up to 5 ppm), and water (50% water cut) contained in the produced hydrocarbons (condensated). For some areas, the hydrocarbon is accompanied by sand, making them erosive as well. These conditions and frequent failures experienced in the field, led to the use of CRA`s. For the wells, 13% Cr and bimetallic (carbon steel/13% Cr) tubing was used for 51 condensate wells containing 5 to 20% CO{sub 2}. For the surface equipment (valves, reducers, expanders and other types of fittings) tungsten carbide hard facing were used, for some of the valves, a epoxi-phenolic coating was used. This article describes the different design criteria used for the installation of the tubing, the logistics involved during field inspections and handling tips to avoid galling during workovers. It also, presents results from the bi-metallic tubing and the hard facings used for the surface equipment.

The space industry has predominantly relied on high gain reflector dish antenna apertures for performing communications, but is constantly investing in phase array antenna concepts to provide increased signal flexibility at reduced system costs in terms of finances and system resources. The problem with traditional phased arrays remains the significantly greater program cost and complexity added to the satellite by integrating arrays of antenna elements with dedicated amplifier and phase shifters to perform adaptive beam forming. Liquid Crystal Reflectarrays (LiCRas) offer some of the electrical beam forming capability of a phased array system with the component and design complexity in lines with a traditional reflector antenna aperture but without the risks associated with mechanical steering systems. The final solution is believed to be a hybrid approach that performs in between the boundaries set by the two current disparate approaches. Practical reflectarrays have been developed since the 90's as a means to control reflection of incident radiation off a flat structure that is electrically curved based on radiating elements and their reflection characteristics with tailored element phase delay. In the last decade several methods have been proposed to enable tunable reflectarrays where the electrical shape of the reflector can be steered by controlling the resonating properties of the elements on the reflector using a DC bias. These approaches range from complex fast switching MEMS and ferroelectric devices, to more robust but slower chemical changes. The aim of this work is to investigate the feasibility of a molecular transition approach in the form of liquid crystals which change permittivity based on the electrical field they are subjected to. In this work, particular attention will be paid to the impact of space environment on liquid crystal reflectarray materials and reflector architectures. Of particular interest are the effects on performance induced by

One of the most startling discoveries in avian molecular phylogenetics is that the volant tinamous are embedded in the flightless ratites, but this topology remains controversial because recent morphological phylogenies place tinamous as the closest relative of a monophyletic ratite clade. Here, we integrate new phylogenomic sequences from 1,448 nuclear DNA loci totaling almost 1 million bp from the extinct little bush moa, Chilean tinamou, and emu with available sequences from ostrich, elegant crested tinamou, four neognaths, and the green anole. Phylogenetic analysis using standard homogeneous models and heterogeneous models robust to common topological artifacts recovered compelling support for ratite paraphyly with the little bush moa closest to tinamous within ratites. Ratite paraphyly was further corroborated by eight independent CR1 retroposon insertions. Analysis of morphological characters reinterpreted on a 27-gene paleognath topology indicates that many characters are convergent in the ratites, probably as the result of adaptation to a cursorial life style. PMID:24825849

More than 60 years after the late Nobel laureate Hannes Alfvén had published a letter stating that oscillating magnetic fields can accelerate ionised matter via magneto-hydrodynamic interactions in a wave like fashion, the technical implementation of Alfvén waves for propulsive purposes has been proposed, patented and examined for the first time by a group of inventors. Consequently improved since then, the name of the latest concept, relying on magneto-acoustic waves to accelerate electric conductive matter, is MOA2—Magnetic field Oscillating Amplified Accelerator. Based on computer simulations, which were undertaken to get a first estimate on the performance of the system, MOA2 is a corrosion free and highly flexible propulsion system, whose performance parameters might easily be adapted in operation, by changing the mass flow and/or the power level. As such the system is capable of delivering a maximum specific impulse of 13116 s (12.87 mN) at a power level of 11.16 kW, using Xe as propellant, but can also be attuned to provide a thrust of 236.5 mN (2411 s) at 6.15 kW of power. First tests—that are further described in this paper—have been conducted successfully with a 400 W prototype system at an ambient pressure of 0.20 Pa, delivered 9.24 mN of thrust at 1472 s ISP, thereby underlining the feasibility of the concept. Based on these results, space propulsion is expected to be a prime application for MOA2—a claim that is supported by numerous applications such as Solar and/or Nuclear Electric Propulsion or even as an 'afterburner system' for Nuclear Thermal Propulsion. However, MOA2 has so far seen most of its R&D impetus from terrestrial applications, like coating, semiconductor implantation and manufacturing as well as steel cutting. Based on this observation, MOA2 resembles an R&D paradigm buster, as it is the first space propulsion system, whose R&D is driven primarily by its terrestrial applications. Different terrestrial applications exist, but

Low-resistance electrical contacts formed on solar cells by melting powders of eutectic composition of semiconductor and dopant. Process improves cell performance without subjecting cell to processing temperatures high enough to degrade other characteristics.

More than 60 years after the later Nobel laureate Hannes Alfven had published a letter stating that oscillating magnetic fields can accelerate ionised matter via magneto-hydrodynamic interactions in a wave like fashion, the technical implementation of Alfven waves for propulsive purposes has been proposed, patented and examined for the first time by a group of inventors. The name of the concept is MOA - Magnetic field Oscillating Amplified thruster. Based on computer simulations, MOA is a highly flexible propulsion system, whose performance parameters might easily be adapted, by changing the mass flow and/or the power level. As such the system is capable to deliver a maximum specific impulse of 13116 s (12.87 mN) at a power level of 11.16 kW, using Xe as propellant, but can also be attuned to provide a thrust of 236.5 mN (2411 s) at 6.15 kW of power. While space propulsion is expected to be the prime application for MOA and is supported by numerous applications such as Solar and/or Nuclear Electric Propulsion or even as an 'afterburner system' for Nuclear Thermal Propulsion, other terrestrial applications can be thought of as well, making the system highly suited for a common space-terrestrial application research and utilisation strategy. This paper presents the recent developments of the MOA Thruster R and D activities at QASAR (www.qasar.at), the company in Vienna, which has been set up to further develop and test the Alfven wave technology and its applications.

A ground base test plan and a specimen evaluation scheme have been developed for the aluminum-copper eutectic solidification experiment to be run in the M518 multipurpose electric furnace during the Skylab mission. Besides thermal and solidification studies a detailed description is given of the quantitative metallographic technique which is appropriate for characterizing eutectic structures. This method should prove a key tool for evaluating specimen microstructure which is the most sensitive indicator of changes produced during solidification. It has been recommended that single grain pre-frozen eutectic specimens be used to simplify microstructural evaluation and to eliminate any porosity in the as-cast eutectic specimens. High purity (99.999%) materials from one supplier should be employed for all experiments. Laboratory studies indicate that porosity occurs in the MRC as-cast eutectic ingots but that this porosity can be eliminated by directional freezing. Chemical analysis shows that the MRC ingots are slightly Al rich and contain about .03% impurity. Because of the impurity content the lower cooldown rate (1.2 C/min) should be used for eutectic freezing if MRC material is used in the M518 furnace.

Knowledge about the diet and ecology of extinct herbivores has important implications for understanding the evolution of plant defence structures, establishing the influences of herbivory on past plant community structure and composition, and identifying pollination and seed dispersal syndromes. The flightless ratite moa (Aves: Dinornithiformes) were New Zealand's largest herbivores prior to their extinction soon after initial human settlement. Here we contribute to the knowledge of moa diet and ecology by reporting the results of a multidisciplinary study of 35 coprolites from a subalpine cave (Euphrates Cave) on the South Island of New Zealand. Ancient DNA analysis and radiocarbon dating revealed the coprolites were deposited by the extinct upland moa (Megalapteryx didinus), and span from at least 6,368±31 until 694±30 (14)C years BP; the approximate time of their extinction. Using pollen, plant macrofossil, and ancient DNA analyses, we identified at least 67 plant taxa from the coprolites, including the first evidence that moa fed on the nectar-rich flowers of New Zealand flax (Phormium) and tree fuchsia (Fuchsia excorticata). The plant assemblage from the coprolites reflects a highly-generalist feeding ecology for upland moa, including browsing and grazing across the full range of locally available habitats (spanning southern beech (Nothofagus) forest to tussock (Chionochloa) grassland). Intact seeds in the coprolites indicate that upland moa may have been important dispersal agents for several plant taxa. Plant taxa with putative anti-browse adaptations were also identified in the coprolites. Clusters of coprolites (based on pollen assemblages, moa haplotypes, and radiocarbon dates), probably reflect specimens deposited at the same time by individual birds, and reveal the necessity of suitably large sample sizes in coprolite studies to overcome potential biases in diet interpretation. PMID:22768206

Co-20.5 at. pct Sn and Ni-21.4 at. pct Si eutectic alloys have been levitated and undercooled in an electromagnetic levitator (EML) and then solidified spontaneously at different undercoolings. The original surface and cross-sectional morphologies of these solidified samples consist of separate eutectic colonies regardless of melt undercooling, indicating that microstructures in the free solidification of the eutectic systems are nucleation controlled. Regular lamellae always grow from the periphery of an independent anomalous eutectic grain in each eutectic colony. This typical morphology shows that the basic unit should be a single eutectic colony, when discussing the solidification behavior. Special emphasis is focused on the anomalous eutectic formation after a significant difference in linear kinetic coefficients is recognized for terminal eutectic phases, in particular when a eutectic reaction contains a nonfaceted disordered solid solution and a faceted ordered intermetallic compound as the terminal eutectic phases. It is this remarkable difference in the linear kinetic coefficients that leads to a pronounced difference in kinetic undercoolings. The sluggish kinetics in the interface atomic attachment of the intermetallic compound originates the occurrence of the decoupled growth of two eutectic phases. Hence, the current eutectic models are modified to incorporate kinetic undercooling, in order to account for the competitive growth behavior of eutectic phases in a single eutectic colony. The critical condition for generating the decoupled growth of eutectic phases is proposed. Further analysis reveals that a dimensionless critical undercooling may be appropriate to show the tendency for the anomalous eutectic-forming ability when considering the difference in linear kinetic coefficients of terminal eutectic phases. This qualitative criterion, albeit crude with several approximations and assumptions, can elucidate most of the published experimental results

We report the cyclic voltammetry, chronoamperometry, and scanning electrochemical microscopy of ferrocene dissolved in deep eutectic solvents (DES), consisting of choline chloride (ChCl) and either trifluoroacetamide (TFA) or malonic acid as the hydrogen-bond donor. Despite the use of ultramicroelectrodes, which were required due to the modest conductivities of the DES employed, linear diffusion behavior was observed in cyclic voltammetric experiments. The high viscosity of 1:2 ChCl/TFA relative to non-aqueous electrochemical solvents leads to a low diffusion coefficient, 2.7 x 10(-8) cm2 s(-1) for ferrocene in this medium. Because of the difficulties in achieving steady-state conditions, SECM approach curves were tip velocity dependent. Under certain conditions, SECM approach curves to an insulating substrate displayed a positive-feedback response. Satisfactory simulation of this unexpected behavior was obtained by including convection terms into the mass transport equations typically used for SECM theory. The observance of positive-feedback behavior at an insulating substrate can be described in terms of a dimensionless parameter, the Peclet number, which is the ratio of the convective and diffusive timescales. Fitting insulator approach curves of ferrocene in 1:2 ChCl/TFA shows an apparent increase in the diffusion coefficient with increasing tip velocity, which can be explained by DES behaving as a shear thinning non-Newtonian fluid. PMID:17973421

The human colonisation of New Zealand in the late thirteenth century AD led to catastrophic impacts on the local biota and is among the most compelling examples of human over-exploitation of native fauna, including megafauna. Nearly half of the species in New Zealand' s pre-human avifauna are now extinct, including all nine species of large, flightless moa (Aves: Dinornithiformes). The abundance of moa in early archaeological sites demonstrates the significance of these megaherbivores in the diet of the first New Zealanders. Combining moa assemblage data, based on DNA identification of eggshell and bone, with morphological identification of bone (literature and museum catalogued specimens), we present the most comprehensive audit of moa to date from several significant 13th-15th century AD archaeological deposits across the east coast of the South Island. Mitochondrial DNA (mtDNA) was amplified from 251 of 323 (78%) eggshell fragments and 22 of 27 (88%) bone samples, and the analyses revealed the presence of four moa species: Anomalopteryx didiformis; Dinornis robustus; Emeus crassus and Euryapteryx curtus. The mtDNA, along with polymorphic microsatellite markers, enabled an estimate of the minimum number of individual eggs consumed at each site. Remarkably, in one deposit over 50 individual eggs were identified - a number that likely represents a considerable proportion of the total reproductive output of moa in the area and emphasises that human predation of all life stages of moa was intense. Molecular sexing was conducted on bones (n = 11). Contrary to previous ancient DNA studies from natural sites that consistently report an excess of female moa, we observed an excess of males (2.7:1), suggestive that males were preferential targets. This could be related to different behaviour between the two highly size-dimorphic sexes in moa. Lastly, we investigated the moa species from recovered skeletal and eggshell remains from seven Wairau Bar burials, and identified

New Zealand offers a unique opportunity to investigate the response of extinct megafaunal ecosystems to major changes in climate and habitat prior to human settlement. Prior to this point (late 13th Century AD) New Zealand contained a diverse avian megafauna dominated by nine species of large flightless ratite moa (Dinornithiformes). We used ancient DNA approaches to generate mitochondrial DNA sequence data from 39 crested moa (Pachyornis australis) and 145 heavy-footed moa (Pachyornis elephantopus) specimens. In combination with radiocarbon dating and dietary isotope analysis we examined the effects of Late Pleistocene and Holocene climate and environmental change on the phylogeography, palaeodemographics, and eventual extinction of Pachyornis. We show that Pachyornis changed altitudinal, longitudinal and latitudinal ranges through the Late Quaternary in response to alterations in the distribution of suitable habitat. However, we found no evidence for large-scale change in population sizes during the past 40,000 radiocarbon years BP (approximately 44,000 calendar years BP), or significant changes in δ13C and δ15N isotope signatures over this time period. The results suggest that crested moa tracked habitat through time with little consequence to population size. For the more broadly distributed heavy-footed moa, changes in climate and habitat distribution may have promoted phylogeographic structuring. Overall this study suggests that the likelihood of megafaunal extinction in New Zealand was greatly reduced in the absence of humans.

The formation of rod eutectic microstructure is investigated systematically in a succinonitrile-camphor alloy of eutectic composition by using the directional solidification technique. A new rod eutectic configuration is observed in which the rods form with elliptical cylindrical shape. Two different orientations of the ellipse are observed that differ by a 90{sup o} rotation such that the major and the minor axes are interchanged. Critical experiments in thin samples, where a single layer of rods forms, show that the spacing and orientation of the elliptic rods are governed by the growth rate and the sample thickness. In thicker samples, multi layers of rods form with circular cross-section and the scaling law between the spacing and velocity predicted by the Jackson and Hunt model is validated. A theoretical model is developed for a two-dimensional array of elliptical rods that are arranged in a hexagonal or a square array, and the results are shown to be consistent with the experimental observations. The model of elliptic rods is also shown to reduce to that for the circular rod eutectic when the lengths of the two axes are equal, and to the lamellar eutectic model when one of the axes is much larger than the other one.

Directional solidification of eutectic alloys shows different types of eutectic morphologies. These include lamellar, rod, oscillating and tilting modes. The growth of these morphologies occurs with a macroscopically planar interface. However, under certain conditions, the planar eutectic front becomes unstable and gives rise to a cellular or a dendritic structure. This instability leads to the cellular/dendritic structure of either a primary phase or a two-phase structure. The objective of this work is to develop a fundamental understanding of the instability of eutectic structure into cellular/dendritic structures of a single phase and of two-phases. Experimental studies have been carried out to examine the transition from a planar to two-phase cellular and dendritic structures in a ceramic system of Alumina-Zirconia (Al{sub 2}O{sub 3}-ZrO{sub 2}) and in a transparent organic system of carbon tetrabromide and hexachloroethane (CBr{sub 4}-C{sub 2}Cl{sub 6}). Several aspects of eutectic interface stability have been examined.

The nucleation mechanism of eutectic grains in hypoeutectic Al-Si foundry alloys has been investigated by examining deep etched specimens in high-resolution field emission gun scanning electron microscope (FEG-SEM) and by using in-situ Focused Ion Beam (FIB) milling and microscopy. Both unmodified and Sr-modified alloys were studied to characterize the nucleation mechanism of eutectic silicon flakes and fibers. It is proposed that following nucleation of eutectic Al on the primary {alpha}-Al dendrites, fine Si particles form at the solidification front upon which the eutectic Si flakes and fibers could develop. The formation of small Si particles is attributed to Si enrichment of the remaining melt due to the formation of eutectic Al (aluminum spikes) at the eutectic temperature. A hypothesis is then proposed to explain the mechanism of eutectic grains formation with main emphasis on the eutectic Si phase.

Samples of Pb-Sn eutectic alloy with a high density of 8.5×103 kg/m3 are levitated with a single-axis acoustic levitator, and containerlessly melted and then solidified in argon atmosphere. High undercoolings up to 38 K are obtained, which results in a microstructural transition of ``lamellas-broken lamellas-dendrites.'' This transition is further investigated in the light of the coupled zone for eutectic growth and the effects of ultrasound. The breaking of regular eutectic lamellas and suppression of gravity-induced macrosegregation of (Pb) and (Sn) dendrites are explained by the complicated internal flow inside the levitated drop, which is jointly induced by the shape oscillation, bulk vibration and rotation of the levitated drop. The ultrasonic field is also found to drive forced surface vibration, which subsequently excites capillary ripples and catalyzes nucleation on the sample surface.

We have made an x-ray study of the Ga-Te eutectic liquid. The phase diagram shows a series of compounds as well as immiscibility regions for two liquid phases and the eutectic. The compounds GaTe and Ga/sub 2/Te/sub 3/ melt congruently. The phase diagram is complicated, and the phase state varies substantially with the component ratio. The liquid eutectic (87 at. % Te) was examined with a high-temperature diffractometer intended particularly for liquids; Cu K..cap alpha.. radiation was used, which was monochromatized with LiF. An integral Fourier transformation was used to calculate the radial distributions for the atoms and the density; the first were used to derive the most likely shortest interatomic distances, while the second gave the mean coordination numbers.

A pseudobinary eutectic alloy composition was determined by a previously developed bleed-out technique. The directionally solidified eutectic alloy with a composition of Ni-37.4Fe-10.0Cr-9.6Al (in wt%) had tensile strengths decreasing from 1,090 MPa at room temperature to 54 MPa at 1,100 C. The low density, excellent microstructural stability, and oxidation resistance of the alloy during thermal cycling suggest that it might have applicability as a gas turbine vane alloy while its relatively low high temperature strength precludes its use as a blade alloy. A zirconium addition increased the 750 C strength, and a tungsten addition was ineffective. The gamma=beta eutectic alloys appeared to obey a normal freezing relation.

Samples of Pb-Sn eutectic alloy with a high density of 8.5 x 10(3) kg/m(3) are levitated with a single-axis acoustic levitator, and containerlessly melted and then solidified in argon atmosphere. High undercoolings up to 38 K are obtained, which results in a microstructural transition of "lamellas-broken lamellas-dendrites." This transition is further investigated in the light of the coupled zone for eutectic growth and the effects of ultrasound. The breaking of regular eutectic lamellas and suppression of gravity-induced macrosegregation of (Pb) and (Sn) dendrites are explained by the complicated internal flow inside the levitated drop, which is jointly induced by the shape oscillation, bulk vibration and rotation of the levitated drop. The ultrasonic field is also found to drive forced surface vibration, which subsequently excites capillary ripples and catalyzes nucleation on the sample surface. PMID:12513291

More than 60 years after the later Nobel laureate Hannes Alfven had published a letter stating that oscillating magnetic fields can accelerate ionised matter via magneto-hydrodynamic interactions in a wave like fashion, the technical implementation of Alfven waves for propulsive purposes has been proposed, patented and examined for the first time by a group of inventors. The name of the concept, utilising Alfven waves to accelerate ionised matter for propulsive purposes, is MOA - Magnetic field Oscillating Amplified thruster. Alfven waves are generated by making use of two coils, one being permanently powered and serving also as magnetic nozzle, the other one being switched on and off in a cyclic way, deforming the field lines of the overall system. It is this deformation that generates Alfven waves, which are in the next step used to transport and compress the propulsive medium, in theory leading to a propulsion system with a much higher performance than any other electric propulsion system. Based on computer simulations, which were conducted to get a first estimate on the performance of the system, MOA is a highly flexible propulsion system, whose performance parameters might easily be adapted, by changing the mass flow and/or the power level. As such the system is capable to deliver a maximum specific impulse of 13116 s (12.87 mN) at a power level of 11.16 kW, using Xe as propellant, but can also be attuned to provide a thrust of 236.5 mN (2411 s) at 6.15 kW of power. While space propulsion is expected to be the prime application for MOA and is supported by numerous applications such as Solar and/or Nuclear Electric Propulsion or even as an 'afterburner system' for Nuclear Thermal Propulsion, other terrestrial applications can be thought of as well, making the system highly suited for a common space-terrestrial application research and utilisation strategy. (authors)

The crystal structure of Escherichia coli MoaB was determined by multiwavelength anomalous diffraction phasing and refined at 1.6 Angstrom resolution. The molecule displayed a modified Rossman fold. MoaB is assembled into a hexamer composed of two trimers. The monomers have high structural similarity with two proteins, MogA and MoeA, from the molybdenum cofactor synthesis pathway in E. Coli, as well as with domains of mammalian gephyrin and plant Cnx1, which are also involved in molybdopterin synthesis. Structural comparison between these proteins and the amino acid conservation patterns revealed a putative active site in MoaB. The structural analysis of this site allowed to advance several hypothesis which can be tested in further studies.

Detection of life on Mars requires definition of a suitable biomarker and development of sensitive yet compact instrumentation capable of performing in situ analyses. Our studies are focused on amino acid analysis because amino acids are more resistant to decomposition than other biomolecules, and because amino acid chirality is a well-defined biomarker. Amino acid composition and chirality analysis has been previously demonstrated in the lab using microfabricated capillary electrophoresis (CE) chips. To analyze amino acids in the field, we have developed the Mars Organic Analyzer (MOA), a portable analysis system that consists of a compact instrument and a novel multi-layer CE microchip.

Collection of three reports describes studies of directional solidification of MnBi/Bi eutectic alloy. Two of the reports, "Influence of Convection on Lamellar Spacing of Eutectics" and "Influence of Convection on Eutectic Microstructure," establish theoretical foundation for remaining document. Reports seek to quantify effect of convection on concentration field of growing lamellar eutectic. Remaining report, "Study of Eutectic Formation," begins by continuing theoretical developments. New technique under development by one of the authors helps to reveal three-dimensional microstructures of alloys.

A mild and efficient synthesis of 2,3-unsaturated sugar derivatives has been achieved by conducting the Ferrier reaction in a deep eutectic solvent (DES). A wide range of alcohols including primary, secondary, benzylic, and sugar-derived primary alcohols can be used. Advantages include good yields, shorter reaction times and recyclability of DES. PMID:26279523

Detached solidification provides a new possibility to grow crystals with improved quality. However, it has not been reproducible. The first part of this dissertation is dedicated to discussion of the mechanisms and conditions that would help to bring detached solidification from a space laboratory to a terrestrial factory. The possibility of a steady-state gap during detached solidification was proved by solving the mass transport and Navier-Stokes equations. A high contact angle of the melt with the ampoule wall, appreciable gas atmosphere, and a low freezing rate are needed to obtain detachment. Stability analysis showed that mass transfer of volatile species from the melt into the gap and heat transfer stabilize detached configuration. In vertical solidification on earth, a convex freezing interface was shown to provide enhanced transport of volatile species towards the gap, and, therefore, supports detachment. The influence of convection on eutectic microstructure selection has been a question for many years. Both experiment and theory have shown that buoyancy-driven convection alone is not enough to explain the difference in microstructure of earth- and space-grown eutectics. The second part of this dissertation is devoted to a study of the influence of temperature oscillations on microstructure selection. Two different models were chosen. The first, a sharp-interface model, was able to give a solution for the excess compositional undercooling for different leading conditions of both lamellar and rod eutectics. The limitation of this model is that it's not able to set the conditions for catastrophic morphological changes. Application of the principle of minimum entropy production to stationary eutectic growth predicts a decrease in eutectic spacing due to freezing rate oscillations. The second, a phase-field model, was developed for the evolution of the microstructure. This phase-field model correctly describes unsteady eutectic solidification, as well as

The crystal structure of a putative molybdenum-cofactor biosynthesis protein C (MoaC) from S. tokodaii (ST0472) was determined at 2.2 Å resolution. The crystal structure of a putative molybdenum-cofactor (Moco) biosynthesis protein C (MoaC) from Sulfolobus tokodaii (ST0472) was determined at 2.2 Å resolution. The crystal belongs to the monoclinic space group C2, with unit-cell parameters a = 123.31, b = 78.58, c = 112.67 Å, β = 118.1°. The structure was solved by molecular replacement using the structure of Escherichia coli MoaC as the probe model. The asymmetric unit is composed of a hexamer arranged as a trimer of dimers with noncrystallographic 32 symmetry. The structure of ST0472 is very similar to that of E. coli MoaC; however, in the ST0472 protein an additional loop formed by the insertion of seven residues participates in intermonomer interactions and the new structure also reveals the formation of an interdimer β-sheet. These features may contribute to the stability of the oligomeric state.

Microbial degradation of N-heterocyclic compounds, including xanthine, quinoline, nicotinate, and nicotine, frequently requires molybdenum hydroxylases. The intramolecular electron transfer chain of molybdenum hydroxylases consists of a molybdenum cofactor, two distinct [2Fe-2S] clusters, and flavin adenine dinucleotide. 3-Succinoylpyridine monooxygenase (Spm), responsible for the transformation from 3-succinoylpyridine to 6-hydroxy-3-succinoylpyridine, is a crucial enzyme in the pyrrolidine pathway of nicotine degradation in Pseudomonas. Our previous work revealed that the heterotrimeric enzyme (SpmA, SpmB, and SpmC) requires molybdopterin cytosine dinucleotide as a cofactor for their activities. In this study, we knocked out four genes, including PPS_1556, PPS_2936, PPS_4063, and PPS_4397, and found that a novel gene, PPS_4397 encoding moaE, is necessary for molybdopterin cytosine dinucleotide biosynthesis. Resting cell reactions of the moaE deletion mutant incubated with 3 g l−1 nicotine at 30 °C resulted in accumulation of 3-succinoylpyridine, and the strain complemented by the moaE gene regained the ability to convert 3-succinoylpyridine. In addition, reverse transcription-quantitative polymerase chain reaction analysis indicated that the transcriptional levels of the genes of moaE, spmA, and spmC of Pseudomonas putida S16 were distinctly higher when grown in nicotine medium than in glycerol medium. PMID:26304596

Arsenic is a globally important pollutant found in the air, food, and in many water systems causing significant human exposure and in some cases illness. While there is no doubt that arsenic is a human carcinogen, there is no consensus on its carcinogenic MOA. Numerous hypotheses...

A two-stage eutectic metal brush assembly having a slip ring rigidly coupled to a shaft, the slip ring being electrically coupled to first voltage polarity. At least one brush is rigidly coupled to a second ring and slidingly engaged to the slip ring. Eutectic metal at least partially fills an annulus between the second ring and a stationary ring. At least one conductor is rigidly coupled to the stationary ring and electrically coupled to a second voltage polarity. Electrical continuity is maintained between the first voltage polarity and the second voltage polarity. Periodic rotational motion is present between the stationary ring and the second ring. Periodic rotational motion is also present between the brush and the slip ring.

Multiple descriptions of the alumina-YAG eutectic crystallography appear in the ceramic literature. The orientation between two phases in a eutectic system has direct impact on residual stress, morphology, microstructural stability, and high temperature mechanical properties. A study to demonstrate that the different crystallographic relationships can be correlated with different growth constraints was undertaken. Fibers produced by Laser-Heated Float Zone (LHFZ) and Edge-defined Film-fed Growth (EFG) were examined. A map of the orientation relationship between Al2O3 and Y3Al5O12 and their relationship to the fiber growth axis as a function of pull rate are presented. Regions in which a single orientation predominates are identified.

We analyze MOA-2010-BLG-311, a high magnification (A{sub max} > 600) microlensing event with complete data coverage over the peak, making it very sensitive to planetary signals. We fit this event with both a point lens and a two-body lens model and find that the two-body lens model is a better fit but with only {Delta}{chi}{sup 2} {approx} 80. The preferred mass ratio between the lens star and its companion is q = 10{sup -3.7{+-}0.1}, placing the candidate companion in the planetary regime. Despite the formal significance of the planet, we show that because of systematics in the data the evidence for a planetary companion to the lens is too tenuous to claim a secure detection. When combined with analyses of other high-magnification events, this event helps empirically define the threshold for reliable planet detection in high-magnification events, which remains an open question.

Detection of life on Mars requires definition of a suitable biomarker and development of sensitive yet compact instrumentation capable of performing in situ analyses. Our studies are focused on amino acid analysis because amino acids are more resistant to decomposition than other biomolecules, and because amino acid chirality is a well-defined biomarker. Amino acid composition and chirality analysis has been previously demonstrated in the lab on microfabricated capillary electrophoresis (CE) chips (1, 2). To analyze amino acids in situ, we have developed the Mars Organic Analyzer (MOA), a portable analysis system that consists of a compact instrument and a novel multi-layer CE microchip. The heart of the MOA is the microchip that contains the CE separation channels as well as microfabricated valves and pumps (3) for sample handling. The pneumatic microfabricated valves are created by combining an etched displacement chamber, an actuated PDMS membrane layer, and a discontinuous fluidic channel structure. A microfabricated pump is created by combining three individually-addressable valves in series. These membrane valves and pumps are integrated with the glass separation channel using a novel multilayer design in which sample enters the top fluidic layer for routing and is directed to the bottom glass layers for CE separation and analysis. The microfabricated device is operated by the portable instrument which contains solenoids for controlling fluidic valves, electronics, a 15 mW 400 nm diode laser, confocal detection optics, and a fiber-optic coupled photomultiplier for fluorescence detection. Limits of detection of fluorescamine-labeled amino acids are in the nM to pM range corresponding to part-per-trillion sensitivities in soil samples (4). The portable CE instrument, in combination with the Mars Organic Detector (MOD) (5), was recently successfully field tested on soil samples rich in jarosite from Panoche Valley, CA. Jarosite has recently been detected on Mars

We report the discovery of MOA-2013-BLG-220Lb, which has a super-Jupiter mass ratio q = 3.01 ± 0.02 × 10{sup –3} relative to its host. The proper motion, μ = 12.5 ± 1 mas yr{sup –1}, is one of the highest for microlensing planets yet discovered, implying that it will be possible to separately resolve the host within ∼7 yr. Two separate lines of evidence imply that the planet and host are in the Galactic disk. The planet could have been detected and characterized purely with follow-up data, which has important implications for microlensing surveys, both current and into the Large Synoptic Survey Telescope (LSST) era.

Global `second-generation' microlensing surveys aim to discover and characterize extrasolar planets and their frequency, by means of round-the-clock high-cadence monitoring of a large area of the Galactic bulge, in a controlled experiment. We report the discovery of a giant planet in microlensing event MOA-2011-BLG-322. This moderate-magnification event, which displays a clear anomaly induced by a second lensing mass, was inside the footprint of our second-generation microlensing survey, involving MOA, OGLE and the Wise Observatory. The event was observed by the survey groups, without prompting alerts that could have led to dedicated follow-up observations. Fitting a microlensing model to the data, we find that the time-scale of the event was tE = 23.2 ± 0.8 d, and the mass ratio between the lens star and its companion is q = 0.028 ± 0.001. Finite-source effects are marginally detected, and upper limits on them help break some of the degeneracy in the system parameters. Using a Bayesian analysis that incorporates a Galactic structure model, we estimate the mass of the lens at 0.39^{+0.45}_{-0.19} M_{⊙}, at a distance of 7.56 ± 0.91 kpc. Thus, the companion is likely a planet of mass 11.6^{+13.4}_{-5.6} M_J, at a projected separation of 4.3^{+1.5}_{-1.2} AU, rather far beyond the snow line. This is the first pure-survey planet reported from a second-generation microlensing survey, and shows that survey data alone can be sufficient to characterize a planetary model. With the detection of additional survey-only planets, we will be able to constrain the frequency of extrasolar planets near their systems' snow lines.

Moa Valles is a well-preserved, likely Amazonian (younger than 2 Ga old), paleodrainage system that is nearly 300 km long and carved into ancient highland terrains west of Idaeus Fossae. The fluvial system apparently originated from fluidized ejecta blankets, and it consists of a series of dam breach paleolakes with associated fan-shaped sedimentary deposits. The paleolakes are interconnected and drain eastward into Liberta crater, forming a complex and multilobate deltaic deposit exhibiting a well-developed channelized distributary pattern with evidence of switching on the delta plain. A breach area, consisting of three spillover channels, is present in the eastern part of the crater rim. These channels connect the Liberta crater to the eastward portion of the valley system, continuing toward Moa Valles with a complex pattern of anabranching channels that is more than 180 km long. Based on hydrological calculations of infilling and spillover discharges of the Liberta crater lake, the formation of the whole fluvial system is compatible with short to medium (<1000 year) timescales, although the length and morphology of the observed fluvial-lacustrine features suggest long-term periods of activity based on terrestrial analogs. Water for the 300 km long fluvial system may have been primarily sourced by the melting of shallow ice due to the thermal anomaly produced by impact craters. The occurrence of relatively recent (likely Amazonian) hydrological activity, which could have been primarily supported by groundwater replenishment, supports the hypothesis that hydrological activity could have been possible after the Noachian-Hesperian boundary, which is commonly considered as the onset epoch of the present cold-dry climate.

This paper presents a new micro-scale model for solidification of eutectic alloys. The model is based on the enthalpy method and simulates the growth of adjacent α and β phases from a melt of eutectic composition in a two-dimensional Eulerian framework. The evolution of the two phases is obtained from the solution of volume averaged energy and species transport equations which are formulated using the nodal enthalpy and concentration potential values. The three phases are tracked using the β-phase fraction and the liquid fraction values in all the computational nodes. Solutal convection flow field in the domain is obtained from the solution of volume-averaged momentum and continuity equations. The governing equations are solved using a coupled explicit-implicit scheme. The model is qualitatively validated with Jackson-Hunt theory. Results show expected eutectic growth pattern and proper species transfer and diffusion field ahead of the interface. Capabilities of the model such as lamella width selection, division of lamella into thinner lamellae and the presence of solutal convection are successfully demonstrated. The present model can potentially be incorporated into the existing framework of enthalpy based micro-scale dendritic solidification models thus leading to an efficient generalized microstructure evolution model.

Ancient DNA was isolated from the bones of 267 individuals of the extinct New Zealand moa (Aves: Dinornithiformes) from two late Holocene deposits [Pyramid Valley (PV) and Bell Hill Vineyard (BHV)] located 5.7 km apart in North Canterbury, South Island. The two sites' combined fossil record cover the last 3000 years of pre-human New Zealand and mitochondrial DNA confirmed that four species ( Dinornis robustus, Euryapteryx curtus, Emeus crassus, and Pachyornis elephantopus) were sympatric in the region. However, the relative species compositions in the two deposits differed significantly with D. robustus and E. crassus being most abundant at PV while E. curtus outnumbered the other three moa taxa combined at BHV. A subsample of 227 individuals had sufficient nuclear DNA preservation to warrant the use of molecular sexing techniques, and the analyses uncovered a remarkable excess of females in both deposits with an overall male to female ratio of 1:5.1. Among juveniles of E. curtus, the only species which was represented by a substantial fraction of juveniles, the sex ratio was not skewed (10 ♂, 10 ♀), suggesting that the observed imbalance arose as a result of differential mortality during maturation. Surprisingly, sex ratios proved significantly different between sites with a 1:2.2 ratio at BHV ( n = 90) and 1:14.2 at PV ( n = 137). Given the mobility of large ratites, and the proximity of the two fossil assemblages in space and time, these differences in taxonomic and gender composition indicate that moa biology and the local environment have affected the fossil representation dramatically and several possible explanations are offered. Apart from adding to our understanding of moa biology, these discoveries reinforce the need for caution when basing interpretation of the fossil record on material from a single site.

The long term goal of this project is to be able to control the microstructure of directionally solidified eutectic alloys, through an improved understanding of the influence of convection. Prior experimental results on the influence of microgravity on the microstructure of fibrous eutectics have been contradictory. Theoretical work at Clarkson University showed that buoyancy-driven convection in the vertical Bridgman configuration is not vigorous enough to alter the concentration field in the melt sufficiently to cause a measurable change in microstructure when the eutectic grows at minimum supercooling. Currently, there are four other hypotheses that might explain the observed changes in microstructure of fibrous eutectics caused by convection: (1) Disturbance of the concentration boundary layer arising from an off-eutectic melt composition and growth at the extremum; (2) Disturbance of the concentration boundary layer of a habit-modifying impurity; (3) Disturbance of the concentration boundary layer arising from an off-eutectic interfacial composition due to non-extremum growth; and (4) A fluctuating freezing rate combined with differences in the kinetics of fiber termination and fiber formation. We favor the last of these hypotheses. Thus, the primary objective of the present grant is to determine experimentally and theoretically the influence of a periodically varying freezing rate on eutectic solidification. A secondary objective is to determine the influence of convection on the microstructure of at least one other eutectic alloy that might be suitable for flight experiments.

A review is given of important developments in the synthesis of oxide-metal eutectic composites and the composite application in the continuing development of field emitters. Known metal oxide-metal binary and ternary eutectic systems are listed. The synthesis, electrical conductivity, thermodynamics, and applications are discussed. (FS)

This paper presents a simple numerical method to calculate the eutectic mixture composition and melting temperature. Using a Newton-Raphson method to solve the nonlinear problem, the calculation is possible for n-component eutectic. We tested this algorithm on inorganic and organic mixtures. A better correlation between experimental and numerical results has been found for organic compound.

Organic semiconductors including rubrene, Alq3, copper phthalocyanine and pentacene are crystallized by the eutectic melt crystallization. Those organic semiconductors form good eutectic systems with the various volatile crystallizable additives such as benzoic acid, salicylic acid, naphthalene and 1,3,5-trichlorobenzene. Due to the formation of the eutectic system, organic semiconductors having originally high melting point (Tm > 300 °C) are melted and crystallized at low temperature (Te = 40.8–133 °C). The volatile crystallizable additives are easily removed by sublimation. For a model system using rubrene, single crystalline rubrene nanowires are prepared by the eutectic melt crystallization and the eutectic-melt-assisted nanoimpinting (EMAN) technique. It is demonstrated that crystal structure and the growth direction of rubrene can be controlled by using different volatile crystallizable additives. The field effect mobility of rubrene nanowires prepared using several different crystallizable additives are measured and compared.

Organic semiconductors including rubrene, Alq3, copper phthalocyanine and pentacene are crystallized by the eutectic melt crystallization. Those organic semiconductors form good eutectic systems with the various volatile crystallizable additives such as benzoic acid, salicylic acid, naphthalene and 1,3,5-trichlorobenzene. Due to the formation of the eutectic system, organic semiconductors having originally high melting point (Tm > 300 °C) are melted and crystallized at low temperature (Te = 40.8–133 °C). The volatile crystallizable additives are easily removed by sublimation. For a model system using rubrene, single crystalline rubrene nanowires are prepared by the eutectic melt crystallization and the eutectic-melt-assisted nanoimpinting (EMAN) technique. It is demonstrated that crystal structure and the growth direction of rubrene can be controlled by using different volatile crystallizable additives. The field effect mobility of rubrene nanowires prepared using several different crystallizable additives are measured and compared. PMID:26976527

Organic semiconductors including rubrene, Alq3, copper phthalocyanine and pentacene are crystallized by the eutectic melt crystallization. Those organic semiconductors form good eutectic systems with the various volatile crystallizable additives such as benzoic acid, salicylic acid, naphthalene and 1,3,5-trichlorobenzene. Due to the formation of the eutectic system, organic semiconductors having originally high melting point (Tm > 300 °C) are melted and crystallized at low temperature (Te = 40.8-133 °C). The volatile crystallizable additives are easily removed by sublimation. For a model system using rubrene, single crystalline rubrene nanowires are prepared by the eutectic melt crystallization and the eutectic-melt-assisted nanoimpinting (EMAN) technique. It is demonstrated that crystal structure and the growth direction of rubrene can be controlled by using different volatile crystallizable additives. The field effect mobility of rubrene nanowires prepared using several different crystallizable additives are measured and compared. PMID:26976527

It is well known that in the liquid state eutectic alloys are theoretically homogeneous under 1 g conditions. However, the homogeneous solidified structure of this alloy is not obtained because thermal convection and non-equilibrium solidification occur. The present investigators have clarified the solidification mechanisms of the eutectic system alloys under 1 g conditions by using the in situ observation method; in particular, the primary crystals of the eutectic system alloys never nucleated in the liquid, but instead did so on the mold wall, and the crystals separated from the mold wall by fluid motion caused by thermal convection. They also found that the equiaxed eutectic grains (eutectic cells) are formed on the primary crystals. In this case, the leading phase of the eutectic must agree with the phase of the primary crystals. In space, no thermal convection occurs so that primary crystals should not move from the mold wall and should not appear inside the solidified structure. Therefore no equiaxed eutectic grains will be formed under microgravity conditions. Past space experiments concerning eutectic alloys were classified into two types of experiments: one with respect to the solidification mechanisms of the eutectic alloys and the other to the unidirectional solidification of this alloy. The former type of experiment has the problem that the solidified structures between microgravity and 1 g conditions show little difference. This is why the flight samples were prepared by the ordinary cast techniques on Earth. Therefore it is impossible to ascertain whether or not the nucleation and growth of primary crystals in the melt occur and if primary crystals influence the formation of the equiaxed eutectic grains. In this experiment, hypo- and hyper-eutectic aluminum copper alloys which are near eutectic point are used. The chemical compositions of the samples are Al-32.4mass%Cu (Hypo-eutectic) and Al-33.5mass%Cu (hyper-eutectic). Long rods for the samples are

This paper reports on the quantification of primary dendritic and secondary eutectic nucleation undercoolings during rapid solidification of impulse atomized hypo-eutectic Al-Cu droplets. The procedure consists in determining the eutectic fraction of each investigated droplet from the fraction of intermetallic Al2Cu obtained by Rietveld refinement analysis of neutrons scattering data. The corresponding eutectic nucleation undercooling is then deduced from the metastable phase diagram of the alloy. The primary dendritic nucleation undercooling is subsequently determined using semi-empirical coarsening models of secondary dendrite arms. The two nucleation undercoolings are finally used as input variables to run a microsegregation model for binary alloys. The fractions of eutectic computed by the microsegregation model compare very favorably with the experimental results.

This paper reports on the quantification of primary dendritic and secondary eutectic nucleation undercoolings during rapid solidification of impulse atomized hypo-eutectic Al-Cu droplets. The procedure consists in determining the eutectic fraction of each investigated droplet from the fraction of intermetallic Al2Cu obtained by Rietveld refinement analysis of neutrons scattering data. The corresponding eutectic nucleation undercooling is then deduced from the metastable phase diagram of the alloy. The primary dendritic nucleation undercooling is subsequently determined using semi-empirical coarsening models of secondary dendrite arms. The two nucleation undercoolings are finally used as input variables to run a microsegregation model for binary alloys. The fractions of eutectic computed by the microsegregation model compare very favorably with the experimental results.

Within the framework of green chemistry, solvents occupy a strategic place. To be qualified as a green medium, these solvents have to meet different criteria such as availability, non-toxicity, biodegradability, recyclability, flammability, and low price among others. Up to now, the number of available green solvents are rather limited. Here we wish to discuss a new family of ionic fluids, so-called Deep Eutectic Solvents (DES), that are now rapidly emerging in the current literature. A DES is a fluid generally composed of two or three cheap and safe components that are capable of self-association, often through hydrogen bond interactions, to form a eutectic mixture with a melting point lower than that of each individual component. DESs are generally liquid at temperatures lower than 100 °C. These DESs exhibit similar physico-chemical properties to the traditionally used ionic liquids, while being much cheaper and environmentally friendlier. Owing to these remarkable advantages, DESs are now of growing interest in many fields of research. In this review, we report the major contributions of DESs in catalysis, organic synthesis, dissolution and extraction processes, electrochemistry and material chemistry. All works discussed in this review aim at demonstrating that DESs not only allow the design of eco-efficient processes but also open a straightforward access to new chemicals and materials. PMID:22806597

The purpose of this study was to investigate the cytotoxic profiles of different ternary natural deep eutectic solvents (NADESs) containing water. For this purpose, five different NADESs were prepared using choline chloride as a salt, alongside five hydrogen bond donors (HBD) namely glucose, fructose, sucrose, glycerol, and malonic acid. Water was added as a tertiary component during the eutectics preparation, except for the malonic acid-based mixture. Coincidentally, the latter was found to be more toxic than any of the water-based NADESs. A trend was observed between the cellular requirements of cancer cells, the viscosity of the NADESs, and their cytotoxicity. This study also highlights the first time application of the conductor-like screening model for real solvent (COSMO-RS) software for the analysis of the cytotoxic mechanism of NADESs. COSMO-RS simulation of the interactions between NADESs and cellular membranes' phospholipids suggested that NADESs strongly interacted with cell surfaces and that their accumulation and aggregation possibly defined their cytotoxicity. This reinforced the idea that careful selection of NADESs components is necessary, as it becomes evident that organic acids as HBD highly contribute to the increasing toxicity of these neoteric mixtures. Nevertheless, NADESs in general seem to possess relatively less acute toxicity profiles than their DESs parents. This opens the door for future large scale utilization of these mixtures. PMID:27386357

We present the discovery of a Neptune-mass planet orbiting a 0.8+/- 0.3{M}ȯ star in the Galactic bulge. The planet manifested itself during the microlensing event MOA-2011-BLG-028/OGLE-2011-BLG-0203 as a low-mass companion to the lens star. The analysis of the light curve provides the measurement of the mass ratio (1.2+/- 0.2)× {10}-4, which indicates that the mass of the planet is 12–60 Earth masses. The lensing system is located at 7.3 ± 0.7 kpc away from the Earth near the direction of Baade’s Window. The projected separation of the planet at the time of the microlensing event was 3.1–5.2 au. Although the microlens parallax effect is not detected in the light curve of this event, preventing the actual mass measurement, the uncertainties of mass and distance estimation are narrowed by the measurement of the source star proper motion on the OGLE-III images spanning eight years, and by the low amount of blended light seen, proving that the host star cannot be too bright and massive. We also discuss the inclusion of undetected parallax and orbital motion effects into the models and their influence onto the final physical parameters estimates. Based on observations obtained with the 1.3 m Warsaw telescope at the Las Campanas Observatory operated by the Carnegie Institution of Washington.

We analyze the planetary microlensing event MOA-2010-BLG-328. The best fit yields host and planetary masses of M {sub h} = 0.11 ± 0.01 M {sub ☉} and M {sub p} = 9.2 ± 2.2 M {sub ⊕}, corresponding to a very late M dwarf and sub-Neptune-mass planet, respectively. The system lies at D {sub L} = 0.81 ± 0.10 kpc with projected separation r = 0.92 ± 0.16 AU. Because of the host's a priori unlikely close distance, as well as the unusual nature of the system, we consider the possibility that the microlens parallax signal, which determines the host mass and distance, is actually due to xallarap (source orbital motion) that is being misinterpreted as parallax. We show a result that favors the parallax solution, even given its close host distance. We show that future high-resolution astrometric measurements could decisively resolve the remaining ambiguity of these solutions.

A planetary microlensing signal is generally characterized by a short-term perturbation to the standard single lensing light curve. A subset of binary-source events can produce perturbations that mimic planetary signals, thereby introducing an ambiguity between the planetary and binary-source interpretations. In this paper, we present the analysis of the microlensing event MOA-2012-BLG-486, for which the light curve exhibits a short-lived perturbation. Routine modeling not considering data taken in different passbands yields a best-fit planetary model that is slightly preferred over the best-fit binary-source model. However, when allowed for a change in the color during the perturbation, we find that the binary-source model yields a significantly better fit and thus the degeneracy is clearly resolved. This event not only signifies the importance of considering various interpretations of short-term anomalies, but also demonstrates the importance of multi-band data for checking the possibility of false-positive planetary signals.

Eutectics are a long known class of multi-component solids with important and useful applications in daily life. In comparison to other multi-component crystalline solids, such as salts, solid solutions, molecular complexes and cocrystals, eutectics are less studied in terms of molecular structure organization and bonding interactions. Classically, a eutectic is defined based on its low melting point compared to the individual components. In this article, we attempt to define eutectics not just based on thermal methods but from a structural organization view point, and discuss their microstructures and properties as organic materials vis-a-vis solid solutions and cocrystals. The X-ray crystal structure of a cocrystal is different from that of the individual components whereas the unit cell of a solid solution is similar to that of one of the components. Eutectics are closer to the latter species in that their crystalline arrangement is similar to the parent components but they are different with respect to the structural integrity. A solid solution possesses structural homogeneity throughout the structure (single phase) but a eutectic is a heterogeneous ensemble of individual components whose crystal structures are like discontinuous solid solutions (phase separated). Thus, a eutectic may be better defined as a conglomerate of solid solutions. A structural analysis of cocrystals, solid solutions and eutectics has led to an understanding that materials with strong adhesive (hetero) interactions between the unlike components will lead to cocrystals whereas those having stronger cohesive (homo/self) interactions will more often give rise to solid solutions (for similar structures of components) and eutectics (for different structures of components). We demonstrate that the same crystal engineering principles which have been profitably utilized for cocrystal design in the past decade can now be applied to make eutectics as novel composite materials, illustrated by

Knowledge about the diet and ecology of extinct herbivores has important implications for understanding the evolution of plant defence structures, establishing the influences of herbivory on past plant community structure and composition, and identifying pollination and seed dispersal syndromes. The flightless ratite moa (Aves: Dinornithiformes) were New Zealand’s largest herbivores prior to their extinction soon after initial human settlement. Here we contribute to the knowledge of moa diet and ecology by reporting the results of a multidisciplinary study of 35 coprolites from a subalpine cave (Euphrates Cave) on the South Island of New Zealand. Ancient DNA analysis and radiocarbon dating revealed the coprolites were deposited by the extinct upland moa (Megalapteryx didinus), and span from at least 6,368±31 until 694±30 14C years BP; the approximate time of their extinction. Using pollen, plant macrofossil, and ancient DNA analyses, we identified at least 67 plant taxa from the coprolites, including the first evidence that moa fed on the nectar-rich flowers of New Zealand flax (Phormium) and tree fuchsia (Fuchsia excorticata). The plant assemblage from the coprolites reflects a highly-generalist feeding ecology for upland moa, including browsing and grazing across the full range of locally available habitats (spanning southern beech (Nothofagus) forest to tussock (Chionochloa) grassland). Intact seeds in the coprolites indicate that upland moa may have been important dispersal agents for several plant taxa. Plant taxa with putative anti-browse adaptations were also identified in the coprolites. Clusters of coprolites (based on pollen assemblages, moa haplotypes, and radiocarbon dates), probably reflect specimens deposited at the same time by individual birds, and reveal the necessity of suitably large sample sizes in coprolite studies to overcome potential biases in diet interpretation. PMID:22768206

We present a simple thermodynamic calculation for a strongly partitioning eutectic system, to examine how the critical nucleus energy changes, depending upon assumptions of the chemical diffusion. The calculations show that for strongly partitioning systems, the maximum undercooling may occur at a composition significantly different than the eutectic composition, particularly if the rate of diffusion is slow in the undercooled state. These simple calculations emphasize the role that partitioning and composition may play in determining optimal compositions in metallic glass systems, which typically occur near (but not at) deep eutectic compositions.

Containerless solidification of Ni-18.7at%Sn eutectic alloy has been achieved with a single-axis acoustic levitator. The temperature, motion, and oscillation of the sample were monitored by a high speed camera. The temperature of the sample can be determined from its image brightness, although the sample moves vertically and horizontally during levitation. The experimentally observed frequency of vertical motion is in good agreement with theoretical prediction. The sample undergoes shape oscillation before solidification finishes. The solidification microstructure of this alloy consists of a mixture of anomalous eutectic plus regular lamellar eutectic. This indicates the achievement of rapid solidification under acoustic levitation condition.

Fiberlike sodium chloride/lithium fluoride eutectic mixtures have been produced on earth and in space by the directional solidification technique. Macroscopic and microscopic examinations were made on longitudinal and transverse sections of Apollo Soyuz Test Project space grown and earth grown ingots. It was found that samples grown in space have a higher percentage of fibers alined with the growth axis. The enhanced alinement of fibers is attributed to the absence of convection currents in the liquid during solidification. Optical transmittance measurements of transverse sections of the space grown and earth grown ingots were performed with an infrared spectrometer. For a given sample thickness, the highest transmittance was obtained from ingots grown in space. For samples of different thicknesses, grown either in space or on earth, it was found that the thinner the sample, the higher the transmittance. This is in agreement with the general optical property of transparent materials.

Pseudobinary eutectic alloys with nominal compositions of Fe-25Ta-22Ni-10Cr and Fe-15.5Nb-14.5Ni-6.0Cr were directionally solidified at 0.5 centimeter per hour. Their microstructure consisted of the fcc, iron solid-solution, matrix phase reinforced by about 41-volume-percent, hcp, faceted Fe2Ta fibers and 41-volume-percent, hcp, Fe2Nb lamellae for the tantalum- and niobium-containing alloys, respectively. The microstructural stability under thermal cycling and the temperature dependence of tensile properties were investigated. These alloys showed low elevated-temperature strength and were not considered suitable for application in aircraft-gas-turbine blades although they may have applicability as vane materials.

Deep eutectic solvents (DESs) have received attention in various applications because of their distinctive properties. In this work, DESs were used as functionalizing agents for graphene due to their potential to introduce new functional groups and cause other surface modifications. Eighteen different types of ammonium- and phosphonium-salt-based DESs were prepared and characterized by FTIR. The graphene was characterized by FTIR, STA, Raman spectroscopy, XRD, SEM, and TEM. Additional experiments were performed to study the dispersion behavior of the functionalized graphene in different solvents. The DESs exhibited both reduction and functionalization effects on DES-treated graphene. Dispersion stability was investigated and then characterized by UV-vis spectroscopy and zeta potential. DES-modified graphene can be used in many applications, such as drug delivery, wastewater treatment, catalysts, composite materials, nanofluids, and biosensors. To the best of our knowledge, this is the first investigation on the use of DESs for graphene functionalization.

Deep eutectic solvents (DESs) have received attention in various applications because of their distinctive properties. In this work, DESs were used as functionalizing agents for graphene due to their potential to introduce new functional groups and cause other surface modifications. Eighteen different types of ammonium- and phosphonium-salt-based DESs were prepared and characterized by FTIR. The graphene was characterized by FTIR, STA, Raman spectroscopy, XRD, SEM, and TEM. Additional experiments were performed to study the dispersion behavior of the functionalized graphene in different solvents. The DESs exhibited both reduction and functionalization effects on DES-treated graphene. Dispersion stability was investigated and then characterized by UV-vis spectroscopy and zeta potential. DES-modified graphene can be used in many applications, such as drug delivery, wastewater treatment, catalysts, composite materials, nanofluids, and biosensors. To the best of our knowledge, this is the first investigation on the use of DESs for graphene functionalization. PMID:26264683

We report the result of the analysis of the light curve of the microlensing event MOA-2009-BLG-016. The light curve is characterized by a short-duration anomaly near the peak and an overall asymmetry. We find that the peak anomaly is due to a binary companion to the primary lens and the asymmetry of the light curve is explained by the parallax effect caused by the acceleration of the observer over the course of the event due to the orbital motion of the Earth around the Sun. In addition, we detect evidence for the effect of the finite size of the source near the peak of the event, which allows us to measure the angular Einstein radius of the lens system. The Einstein radius combined with the microlens parallax allows us to determine the total mass of the lens and the distance to the lens. We identify three distinct classes of degenerate solutions for the binary lens parameters, where two are manifestations of the previously identified degeneracies of close/wide binaries and positive/negative impact parameters, while the third class is caused by the symmetric cycloid shape of the caustic. We find that, for the best-fit solution, the estimated mass of the lower-mass component of the binary is (0.04 {+-} 0.01) M{sub sun}, implying a brown-dwarf companion. However, there exists a solution that is worse only by {Delta}{chi}{sup 2} {approx} 3 for which the mass of the secondary is above the hydrogen-burning limit. Unfortunately, resolving these two degenerate solutions will be difficult as the relative lens-source proper motions for both are similar and small ({approx}1 mas yr{sup -1}) and thus the lens will remain blended with the source for the next several decades.

Hydrolases show good catalytic activity in deep eutectic solvents, despite the presence of urea, which can denature enzymes, or alcohols, which can interfere with hydrolase-catalyzed reactions. PMID:18309428

This grant began in June of 1996. Its long term goal is to be able to control the microstructure of directionally solidified eutectic alloys, through an improved understanding of the influence of convection. The primary objective of the projects in the present grant is to test hypotheses for the reported influence of microgravity on the microstructure of eutectics. The prior experimental results on the influence of microgravity on the microstructure of eutectics have been contradictory. With lamellar eutectics, microgravity had a negligible effect on the microstructure. Microgravity experiments with fibrous eutectics sometimes showed a finer microstructure and sometimes a coarser microstructure. Most research has been done on the MnBi/Bi rod-like eutectic. Larson and Pirich obtained a two-fold finer microstructure both from microgravity and by use of a magnetic field to quench buoyancy-driven convection. Smith, on the other hand, observed no change in microgravity. Prior theoretical work at Clarkson University showed that buoyancy-driven convection in the vertical Bridgman configuration is not vigorous enough to alter the concentration field in front of a growing eutectic sufficiently to cause a measurable change in microstructure. We assumed that the bulk melt was at the eutectic composition and that freezing occurred at the extremum, i.e. with minimum total undercooling at the freezing interface. There have been four hypotheses attempting to explain the observed changes in microstructure of fibrous eutectics caused by convection: I .A fluctuating freezing rate, combined with unequal kinetics for fiber termination and branching. 2. Off-eutectic composition, either in the bulk melt due to an off-eutectic feed or at the freezing interface because of departure from the extremum condition. 3. Presence of a strong habit modifying impurity whose concentration at the freezing interface would be altered by convection. At the beginning of the present grant, we favored the

A novel technique resulting in large undercoolings in bulk samples (23g) of lead-tin eutectic alloy is described. Samples of eutectic composition were processed with undercoolings ranging from 4 to 20 K and with cooling rates varying between 0.04 to 4 K/sec. The final macrostructure of undercooled samples depends on both the initial undercooling of the melt and the cooling rate. Gravity-driven segregation is found to increase with increasing undercooling. A eutectic Pb-Sn alloy undercooled at 20 K and cooled at 4 K/sec had a composition of about Pb-72 wt pct Sn at the top and 55 pct Sn at the bottom. Macrosegregation in these undercooled lead-tin eutectic alloys is shown to be primarily due to a sink/float mechanism caused by the difference in density of the solid and liquid phases and the undercooling and nucleation behavior of the alloy.

Eutectic compositions and congruently melting intermetallic compounds in binary and multicomponent systems among common elements such as Al, Ca, Cu, Mg, P, Si, and Zn may be useful for high temperature heat storage. In this work, heats of fusion of new multicomponent eutectics and intermetallic phases are reported, some of which are competitive with molten salts in heat storage density at high temperatures. The method used to determine unknown eutectic compositions combined results of differential thermal analysis, metallography, and microprobe analysis. The method allows determination of eutectic compositions in no more than three steps. The heats of fusion of the alloys were measured using commercial calorimeters, a differential thermal analyzer, and a differential scanning calorimeter.

This paper describes a three-dimensional numerical model to study the influence of convection on the rod-like microstructure of an eutectic system. This model is based on a central finite difference approach. By applying it, the average concentration near the solid/liquid interface of a growing rod-like eutectic was determined for eutectic compositions C(e) of 0.03, 0.05, and 0.10. Following Jackson and Hunt (1966), the average interfacial composition was converted to a change of undercooling at the interface and, finally, to spacing between the rods. The change in rod spacing with increasing intensity of convection was calculated assuming the eutectic grows at minimum interfacial undercooling. It was confirmed that an increase in convection should coarsen the microstructure (i.e., the rod spacing increases with increasing intensity of stirring).

The dynamics of rod-like eutectics are examined using a directional solidification setup, which allows real-time observation of the whole solidification front in specimens of transparent eutectic alloys -here, succinonitrile-(D)camphor. In steady-state, rod eutectic growth patterns consist of triangular arrays, more or less disturbed by topological defects. In the absence of strong convection and of crystallographic anisotropy, the long-time evolution of the pattern is dominated by "imperfections" of the system, such as misalignment of the temperature gradient, and finite-size. In this study, we present experimental results on the finite-size effects on rod eutectics and show that a rod to lamella transition takes place as a result of finite-size effect only, at a given alloy concentration.

We report on the analysis of the high microlensing event MOA-2008-BLG-379, which has a strong microlensing anomaly at its peak due to a massive planet with a mass ratio of q = 6.9 × 10{sup –3}. Because the faint source star crosses the large resonant caustic, the planetary signal dominates the light curve. This is unusual for planetary microlensing events, and as a result, the planetary nature of this light curve was not immediately noticed. The planetary nature of the event was found when the Microlensing Observations in Astrophysics (MOA) Collaboration conducted a systematic study of binary microlensing events previously identified by the MOA alert system. We have conducted a Bayesian analysis based on a standard Galactic model to estimate the physical parameters of the lens system. This yields a host star mass of M{sub L}=3.3{sub −1.2}{sup +1.7} M{sub ⊙} orbited by a planet of mass m{sub P}=0.56{sub −0.27}{sup +0.24} M{sub Jup} at an orbital separation of a=3.3{sub −1.2}{sup +1.3} AU at a distance of D{sub L}=4.1{sub −1.9}{sup +1.7} kpc. The faint source magnitude of I {sub S} = 21.30 and relatively high lens-source relative proper motion of μ{sub rel} = 7.6 ± 1.6 mas yr{sup –1} imply that high angular resolution adaptive optics or Hubble Space Telescope observations are likely to be able to detect the source star, which would determine the masses and distance of the planet and its host star.

Directionally solidified eutectic alloys of the system MnBi/Bi have been investigated with reference to the dependence of the fiber spacing on the growth rate and the interfacial temperature gradient. It is found that the fiber spacing varies as the inverse square root of the growth rate and does not depend on the temperature gradient in contrast to the claims that all faceted/non-faceted eutectics should show a temperature gradient influence.

Lamellar eutectic growth was investigated in the transparent organic alloy neopentylglycol-(D)camphor of eutectic composition (NPG-45.3 wt% DC) using bulk (3D) and thin (2D) samples. Two types of eutectic grains were observed in the polycrystalline samples, either with lamellae well aligned to the direction of solidification or inclined at an angle of 21.5±1.5°. The well aligned grains were used for determining lamellar spacing as function of growth velocity V and temperature gradient G. Based on these data the Jackson-Hunt constant was evaluated to be KJH=1.60±0.15 μm3 s-1. For low growth velocity experiments the contact angles for (DC) and (NPG) lamellae at eutectic triple junctions were also evaluated, being θ(DC)=50.9±4.1° and θ(NPG)=41.8±4.7°, respectively. Using these values, as well as phase diagram data and the Gibbs-Thomson coefficients, the chemical coefficient of diffusion of (D)camphor in the eutectic liquid at eutectic temperature 53 °C was estimated to be DL=97±15 μm2 s-1.

We present an experimental investigation of the morphological transition of lamellar eutectic growth fronts called ``formation of eutectic colonies'' by the method of thin-sample directional solidification of a transparent model alloy, CBr4-C2Cl6. This morphological transition is due to the presence in the melt of traces of chemical components other than those of the base binary alloy (impurities). In this study, we use naphthalene as an impurity. The formation of eutectic colonies has generally been viewed as an impurity-driven Mullins-Sekerka instability of the envelope of the lamellar front. This traditional view neglects the strong interaction existing between the Mullins-Sekerka process and the dynamics of the lamellar pattern. This investigation brings to light several original features of the formation of eutectic colonies, in particular, the emission of long-wavelength traveling waves, and the appearance of dendritelike structures called two-phase fingers, which are connected with this interaction. We study the part played by these phenomena in the transition to eutectic colonies as a function of the impurity concentration. Recent theoretical results on the linear stability of ternary lamellar eutectic fronts [Plapp and Karma, Phys. Rev. E 60, 6865 (1999)] shed light on some aspects of the observed phenomena.

The eutectic is one of only three solidification classes that exist. The others are isostructural and peritectic-class reactions, respectively. Simplistically, in a binaryeutectic phase diagram, a single liquid phase isothermally decomposes to two solid phases in a cooperative manner. The melting point minimum at the eutectic composition, isothermal solidification temperature, near-isocompositional solidification and refined solidification microstructure lend themselves naturally to such applications as brazing and soldering; industries that eutectic alloys dominate. Interest in direct process control of microstructures has led, more recently, to in-situ eutectic directional solidification with applications in electro-magnetics and electro-optics. In these cases, controlled structural refinement and the high aspect ratio and regularity of the distributed eutectic phases is highly significant to the fabrication and application of these in-situ natural composites. The natural pattern formation and scaling of the dispersed phase on a sub-micron scale has enormous potential application, since fabricating bulk materials on this scale mechanically has proven to be particularly difficult. It is thus of obvious importance to understand the solidification of eutectic materials since they are of great commercial significance. The dominant theory that describes eutectic solidification was derived for diffusion-controlled growth of alloys where both solid eutectic phases solidify metallically, i.e. without faceting at the solidification interface. Both high volume fraction (lamellar) and low volume fraction (rod-like) regular metallic arrays are treated by this theory. Many of the useful solders and brazements, however, and most of the regular in-situ composites are characterized by solidification reactions that are faceted/non-faceted in nature, rather than doubly non-faceted (metallic). Further, diffusion-controlled growth conditions are atypical terrestrially since

By analysing ancient DNA (aDNA) from 74 (14)C-dated individuals of the extinct South Island giant moa (Dinornis robustus) of New Zealand, we identified four dyads of closely related adult females. Although our total sample included bones from four fossil deposits located within a 10 km radius, these eight individuals had all been excavated from the same locality. Indications of kinship were based on high pairwise genetic relatedness (rXY) in six microsatellite markers genotyped from aDNA, coupled with overlapping radiocarbon ages. The observed rXY values in the four dyads exceeded a conservative cutoff value for potential relatives obtained from simulated data. In three of the four dyads, the kinship was further supported by observing shared and rare mitochondrial haplotypes. Simulations demonstrated that the proportion of observed dyads above the cutoff value was at least 20 times higher than expected in a randomly mating population with temporal sampling, also when introducing population structure in the simulations. We conclude that the results must reflect social structure in the moa population and we discuss the implications for future aDNA research. PMID:26039408

One of the challenges in antibiotic lead discovery is the difficulty and time-consuming task of determining the mechanism of action (MOA) of antibacterial compounds. In this report, we describe the development and validation of a facile and inexpensive assay system utilizing disk diffusion of inhibitors on solid agar medium embedded with mixed pools of a comprehensive collection of Escherichia coli clones each containing a plasmid-borne inducible essential gene from E. coli. From individual clones, pilot small-scale (48 or 50 clones) assays, to full-scale target identification platform for antibacterials (TIPA) system, involving a variety of assay formats (liquid vs solid media, individual vs mix clones), we demonstrate that elevated resistance phenotypes of relevant cell clones were highly specific. In particular, the TIPA system was able to reveal cellular targets of several known antibacterial inhibitors: cerulenin, diazaborine, indolmycin, phosphomycin, and triclosan. Complementary to several existing MOA profiling schemes, the TIPA system offers a simple and low-cost method for elucidating the target proteins of antibacterial inhibitors, thus will facilitate discovery and development of novel antibacterial compounds to combat multidrug-resistant bacterial pathogens. PMID:24622888

We report the detection of sub-Saturn-mass planet MOA-2008-BLG-310Lb and argue that it is the strongest candidate yet for a bulge planet. Deviations from the single-lens fit are smoothed out by finite-source effects and therefore are not immediately apparent from the light curve. Nevertheless, we find that a model in which the primary has a planetary companion is favored over the single-lens model by DELTAchi{sup 2} {approx} 880 for an additional 3 degrees of freedom. Detailed analysis yields a planet/star mass ratio q = (3.3 +- 0.3) x 10{sup -4} and an angular separation between the planet and star within 10% of the angular Einstein radius. The small angular Einstein radius, theta{sub E} = 0.155 +- 0.011 mas, constrains the distance to the lens to be D{sub L} >6.0 kpc if it is a star (M{sub L} >0.08 M{sub sun}). This is the only microlensing exoplanet host discovered so far that must be in the bulge if it is a star. By analyzing VLT NACO adaptive optics images taken near the baseline of the event, we detect additional blended light that is aligned to within 130 mas of the lensed source. This light is plausibly from the lens, but could also be due to a companion to the lens or source, or possibly an unassociated star. If the blended light is indeed due to the lens, we can estimate the mass of the lens, M{sub L} = 0.67 +- 0.14 M{sub sun}, planet mass m = 74 +- 17 M{sub +}, and projected separation between the planet and host, 1.25 +- 0.10 AU, putting it right on the 'snow line'. If not, then the planet has lower mass, is closer to its host and is colder. To distinguish among these possibilities on reasonable timescales would require obtaining Hubble Space Telescope images almost immediately, before the source-lens relative motion of mu= 5 mas yr{sup -1} causes them to separate substantially.

In continuation of investigation for environmentally benign protocol for new solvents termed deep eutectic solvents (DESs), it is herein reported results concerning the toxicity and cytotoxicity of choline chloride (ChCl) based DESs with four hydrogen bond donors including glycerine, ethylene glycol, triethylene glycol and urea. The toxicity was investigated using two Gram positive bacteria Bacillus subtilis and Staphylococcus aureus, and two Gram negative bacteria Escherichia coli and Pseudomonas aeruginosa. The cytotoxicity effect was tested using the Artemia salina leach. It was found that there was no toxic effect for the tested DESs on all of the studied bacteria confirming their benign effects on these bacteria. Nevertheless, it was found that the cytotoxicity of DESs was much higher than their individual components (e.g. glycerine, ChCl) indicating that their toxicological behavior is different. For our best knowledge this is the first time that toxicity and cytotoxicity of DESs were studied. The toxicity and cytotoxicity of DESs varied depending on the structure of components. Careful usage of the terms non-toxicity and biodegradability must be considered. More investigation on this matter is required. PMID:23200570

When the MnBi-Bi eutectic is directionally solidified, it forms fibers of MnBi in a matrix of bismuth. When the material solidified in space at rates of 30 and 50 cm/hr, the average fiber spacing lambda was about one half of the value obtained in cases in which the same material solidified on earth. Neither an altered temperature gradient nor a fluctuating freezing rate are apparently responsible for the change in lambda, and the possibility is studied that natural convection increases lambda on earth by perturbing the compositional field in the melt ahead of the growing solid. A theoretical analysis is conducted along with some experiments. On the basis of the theoretical results for lamellar growth, it is concluded that the spacing lambda increases with increasing stirring, especially at small freezing rates. The experiments indicate that at low growth rates the cross-sectional area of the MnBi blades increases with increased stirring and with decreased growth rate.

The Belgian Nuclear Research Centre (SCK.CEN) is in the process of designing MYRRHA, a new multi-purpose irradiation facility to replace the ageing BR2. MYRRHA is a fast spectrum reactor cooled with lead-bismuth eutectic (LBE). As liquid metal is opaque to visual light, ultrasonic measurement techniques are selected to fulfill essential tasks that, according to our assessment, will be demanded by licensing authorities, in particular: fuel assembly identification and localization of a lost fuel assembly. To that end, a considerable research effort at SCK.CEN is devoted to study ultrasonic propagation in LBE. As ultrasonic experiments in LBE are elaborate and expensive to set up, we are particularly interested in to what extent experiments in water can be extrapolated to LBE - one of the main focuses of this article. We describe and present results of a first experiment with this goal which shows that the signal to noise ratio is better in LBE and that we even see small diffuse reflections up to 40 deg. off normal. On the other hand, we do not see internal reflections in stainless steel objects in LBE which we do in water. Therefore, we conclude that experiments in water can be used to validate algorithms for LBE on the condition that they do not rely on internal reflections. We also present solutions to tackle the essential tasks: fuel assembly identification and lost object localization. The requirements for the ultrasonic equipment implementing these solutions are also discussed. (authors)

In this article, we report a molecular dynamics simulation study on the X-ray and neutron scattering structures of deep eutectic solvents (DESs) and show that the DESs studied possess unique spatial heterogeneity on molecular length scales. The simulated X-ray and neutron scattering structure functions (S(q)s) of the DESs made of alkylamide + Li(+)/ClO4(-) display two peaks in the intermolecular region of the S(q)s. As a signature of nanoscale structural organization/heterogeneity, a prepeak is observed at 0.1 < q/Å(-1) < 0.4. The principal peak observed at around 1.2 < q/Å(-1) < 2 is rendered by short-distance inter- and intraspecies correlations. For the DESs studied, we demonstrate that nanoscale spatial heterogeneity is exhibited profoundly by the segregated domains of the constituent electrolyte, and the principal peak in S(q) is because of all sorts of close-contact correlations. The extent of nanoscale morphology as well as the strength of ion pairing is enhanced for the longer-tail alkylamide DES. PMID:27314310

A general multidimensional model of alloy solidification is presented in which a velocity-dependent freezing temperature is coupled with the macroscale energy equation. The velocity dependence of the freezing temperature ( Tf˜v ) results from the microscale species diffusion for microstructures with coupled eutectic growth. At solidification rates ( ˜ 1--10 mm/s) that are representative of gravity permanent mold and die casting processes, consideration of the nonequilibrium conditions at the interface affects the prediction of the macroscale thermal field. Near-eutectic alloys freeze with a macroscopically discrete solid-liquid interface at a temperature below the equilibrium eutectic temperature. The model is illustrated with unidirectional solidification of a near-eutectic alloy in a finite domain and solved numerically with a fixed-grid Galerkin finite element method. The numerical algorithm includes inexpensive steps to compute the interface speed explicitly. By nondimensionalizing the governing equations the effect of coupled eutectic growth on heat transport is clearly identified so that the model's sensitivity to important parameters can be investigated. Additionally, the average eutectic spacing can be determined with the temperature field, rather than post-determination from a standard, uncoupled solution of the energy equation. The eutectic coupling results indicate that the predicted solid-liquid interface location lags behind the uncoupled solution; therefore, decreasing the amount of solid formed, increasing the total solidification time, and increasing the average eutectic spacing. A procedure is also illustrated for computing mechanical properties using experimental correlations and the computed interface velocity history. The effect of the eutectic undercooling is then studied in a square domain and a realistic three-dimensional production casting geometry. In order to address the multidimensional cases, a phase-field formulation is developed

Deep eutectic solvents, as a new type of eco-friendly solvent, have attracted increasing attention in chemistry for the extraction and separation of target compounds from various samples. To summarize the application of deep eutectic solvents, this review highlights some of the unique properties of deep eutectic solvents and deep-eutectic-solvent-based materials, as well as their applications in extraction and separation. In this paper, the available data and references in this field are reviewed to summarize the application developments of deep eutectic solvents. Based on the development of deep eutectic solvents, the exploitation of new deep eutectic solvents and deep-eutectic-solvent-based materials are expected to diversify into extraction and separation. PMID:25581398

BACKGROUND Huntington's disease (HD) is a dominantly inherited disease caused by a CAG expansion mutation in HTT. The age at onset of clinical symptoms is determined primarily by the length of this CAG expansion but is also influenced by other genetic and/or environmental factors. OBJECTIVE Recently, through genome-wide association studies (GWAS) aimed at discovering genetic modifiers, we identified loci associated with age at onset of motor signs that are significant at the genome-wide level. However, many additional HD modifiers may exist but may not have achieved statistical significance due to limited power. METHODS In order to disseminate broadly the entire GWAS results and make them available to complement alternative approaches, we have developed the internet website "GeM MOA" where genetic association results can be searched by gene name, SNP ID, or genomic coordinates of a region of interest. RESULTS Users of the Genetic Modifiers of Motor Onset Age (GeM MOA) site can therefore examine support for association between any gene region and age at onset of HD motor signs. GeM MOA's interactive interface also allows users to navigate the surrounding region and to obtain association p-values for individual SNPs. CONCLUSIONS Our website conveys a comprehensive view of the genetic landscape of modifiers of HD from the existing GWAS, and will provide the means to evaluate the potential influence of genes of interest on the onset of HD. GeM MOA is freely available at https://www.hdinhd.org/. PMID:26444025

Papain-like cysteine proteases (PLCPs) constitute the largest group of thiol-based protein degrading enzymes and are characterized by a highly conserved fold. They are found in bacteria, viruses, plants and animals and involved in a number of physiological and pathological processes, parasitic infections and host defense, making them interesting targets for drug design. The Marasmius oreades agglutinin (MOA) is a blood group B-specific fungal chimerolectin with calcium-dependent proteolytic activity. The proteolytic domain of MOA presents a unique structural arrangement, yet mimicking the main structural elements in known PLCPs. Here we present the X-ray crystal structure of MOA in complex with Z-VAD-fmk, an irreversible caspase inhibitor known to cross-react with PLCPs. The structural data allow modeling of the substrate binding geometry and mapping of the fundamental enzyme-substrate interactions. The new information consolidates MOA as a new, yet strongly atypical member of the papain superfamily. The reported complex is the first published structure of a PLCP in complex with the well characterized caspase inhibitor Z-VAD-fmk. PMID:26901797

A directionally solidified multivariant eutectic gamma-gamma prime nickel-base superalloy casting having improved high temperature properties was developed. The alloy is comprised of a two phase eutectic structure consisting essentially of on a weight percent base, 6.0 to 9.0 aluminum, 5.0 to 17.0 tantalum, 0-10 cobalt, 0-6 vanadium, 0-6 rhenium, 2.0-6.0 tungsten, and the balance being nickel, subject to the proviso that the sum of the atomic percentages of aluminum plus tantalum is within the range of from 19-22, and the ratio of atomic percentages of tantalum to aluminum plus tantalum is within the range of from 0.12 to 0.23. Embedded within the gamma nickel-base matrix are aligned eutectic gamma prime phase (primarily nickel-aluminum-tantalum) reinforcing fibers.

In this paper, we report our results using eutectic bonding with the aluminum/germanium alloy to create high quality bonds. The results of a series of experiments conducted to optimize eutectic alloy bonding for MEMS are described. Issues discussed include surface preparation, eutectic composition, bonding apparatus and bonding conditions (temperature and time).

Extending previous work [Pusztai et al., Phys. Rev. E 87, 032401 (2013)], we have studied the formation of eutectic dendrites in a model ternary system within the framework of the phase-field theory. We have mapped out the domain in which two-phase dendritic structures grow. With increasing pulling velocity, the following sequence of growth morphologies is observed: flat front lamellae → eutectic colonies → eutectic dendrites → dendrites with target pattern → partitionless dendrites → partitionless flat front. We confirm that the two-phase and one-phase dendrites have similar forms and display a similar scaling of the dendrite tip radius with the interface free energy. It is also found that the possible eutectic patterns include the target pattern, and single- and multiarm spirals, of which the thermal fluctuations choose. The most probable number of spiral arms increases with increasing tip radius and with decreasing kinetic anisotropy. Our numerical simulations confirm that in agreement with the assumptions of a recent analysis of two-phase dendrites [Akamatsu et al., Phys. Rev. Lett. 112, 105502 (2014)], the Jackson-Hunt scaling of the eutectic wavelength with pulling velocity is obeyed in the parameter domain explored, and that the natural eutectic wavelength is proportional to the tip radius of the two-phase dendrites. Finally, we find that it is very difficult/virtually impossible to form spiraling two-phase dendrites without anisotropy, an observation that seems to contradict the expectations of Akamatsu et al. Yet, it cannot be excluded that in isotropic systems, two-phase dendrites are rare events difficult to observe in simulations. PMID:25903891

Extending previous work [Pusztai et al., Phys. Rev. E 87, 032401 (2013)], we have studied the formation of eutectic dendrites in a model ternary system within the framework of the phase-field theory. We have mapped out the domain in which two-phase dendritic structures grow. With increasing pulling velocity, the following sequence of growth morphologies is observed: flat front lamellae → eutectic colonies → eutectic dendrites → dendrites with target pattern → partitionless dendrites → partitionless flat front. We confirm that the two-phase and one-phase dendrites have similar forms and display a similar scaling of the dendrite tip radius with the interface free energy. It is also found that the possible eutectic patterns include the target pattern, and single- and multiarm spirals, of which the thermal fluctuations choose. The most probable number of spiral arms increases with increasing tip radius and with decreasing kinetic anisotropy. Our numerical simulations confirm that in agreement with the assumptions of a recent analysis of two-phase dendrites [Akamatsu et al., Phys. Rev. Lett. 112, 105502 (2014)], the Jackson-Hunt scaling of the eutectic wavelength with pulling velocity is obeyed in the parameter domain explored, and that the natural eutectic wavelength is proportional to the tip radius of the two-phase dendrites. Finally, we find that it is very difficult/virtually impossible to form spiraling two-phase dendrites without anisotropy, an observation that seems to contradict the expectations of Akamatsu et al. Yet, it cannot be excluded that in isotropic systems, two-phase dendrites are rare events difficult to observe in simulations.

The Jackson-Hunt model of eutectic growth is extended to allow for different densities of the phases. The density differences give rise to fluid flow which is calculated from a series solution of the fluid flow equations in the Stokes flow approximation. The solute diffusion equation with flow terms is then solved numerically using an adaptive refinement and multigrid algorithm (PLTMG). The interface undercoolings and volume fractions are calculated as a function of spacing for tin-lead and iron-carbon eutectic alloys and for an aluminum-indium monotectic alloy. The numerical results are compared with various approximations based on the Jackson-Hunt analysis.

The Jackson-Hunt model of eutectic growth is extended to allow for different densities of the phases. The density differences give rise to fluid flow which is calculated from a series solution of the fluid flow equations in the Stokes flow approximation. The solute diffusion equation with flow terms is then solved numerically using an adaptive refinement and multigrid algorithm. The interface undercoolings and volume fractions are calculated as a function of spacing for tin-lead and iron-carbon eutectic alloys and for an aluminum-indium monotectic alloy. The numerical results are compared with various approximations based on the Jackson-Hunt analysis.

We report a route to synthesize a wide range of organophosphates of biological significance in a deep eutectic solvent (2:1 urea and choline chloride), utilizing various orthophosphate sources. Heating an organic alcohol in the solvent along with a soluble phosphorus source yields phosphorus esters of choline as well as that of the added organic in yields between 15 to 99 %. In addition, phosphite analogs of biological phosphates and peptides were also formed by the simple mixing of reagents and heating at 60-70 °C in the deep eutectic solvent. The presented dehydration reactions are relevant to prebiotic and green chemistry in alternative solvents. PMID:24368625

A simple deep eutectic solvent based on tin (II) chloride was used as a dual catalyst and environmentally benign reaction medium for an efficient synthesis of 3,4-dihydropyrimidin-2(1H)-one derivatives, from aromatic and aliphatic aldehydes, 1,3-dicarbonyl compounds, and urea in good-to-excellent yields and short reaction time. This simple ammonium deep eutectic solvent, easily synthesized from choline chloride and tin chloride, is relatively inexpensive and recyclable, making it applicable for industrial applications. PMID:22649326

A simple deep eutectic solvent based on tin (II) chloride was used as a dual catalyst and environmentally benign reaction medium for an efficient synthesis of 3,4-dihydropyrimidin-2(1H)-one derivatives, from aromatic and aliphatic aldehydes, 1,3-dicarbonyl compounds, and urea in good-to-excellent yields and short reaction time. This simple ammonium deep eutectic solvent, easily synthesized from choline chloride and tin chloride, is relatively inexpensive and recyclable, making it applicable for industrial applications. PMID:22649326

In order to develop a resolution procedure for a given racemic compound, the first and the most important step is finding the most suitable resolving agent. We studied 18 individual resolutions that were carried out with resolving agents having high eutectic composition. We found that very high enantiomeric excess values were obtained in all cases. We assume that the eutectic composition of a given resolving agent is one of the most important properties that should always be considered during the search for the most efficient resolving agent. PMID:26797938

Deep eutectic mixtures of levulinic acid with a systematic series of imidazoles are measured by broadband dielectric spectroscopy, differential scanning calorimetry, and Fourier transform infrared spectroscopy to investigate the impact of steric interactions on charge transport and structural dynamics. An enhancement of dc conductivity is found in each of the imidazoles upon the addition of levulinic acid. However, the extent of increase is dependent upon the alkyl substitution on the imidazole ring. These results highlight the importance of molecular structure on hydrogen bonding and charge transport in deep eutectic mixtures.

A small lead-bismuth eutectic-cooled reactor concept (referred to as the Hyperion reactor concept) is being studied at Los Alamos National Laboratory and Hyperion Power Generation. In this report, a critical assessment of the lead-bismuth eutectic technology for Hyperion reactor is presented based on currently available knowledge. Included are: material compatibility, oxygen control, thermal hydraulics, polonium control. The key advances in the technology and their applications to Hyperion reactor design are analyzed. Also, the near future studies in main areas of the technology are recommended for meeting the design requirements.

The objectives of this study are to: identify appropriate eutectic salt mixture catalysts for coal gasification; assess agglomeration tendency of catalyzed coal; evaluate various catalyst impregnation techniques to improve initial catalyst dispersion; evaluate effects of major process variables (such as temperature, system pressure, etc.) on coal gasification; evaluate the recovery, regeneration and recycle of the spent catalysts; and conduct an analysis and modeling of the gasification process to provide better understanding of the fundamental mechanisms and kinetics of the process. A review of the collected literature was carried out. The catalysts which have been used for gasification can be roughly classified under the following five groups: alkali metal salts; alkaline earth metal oxides and salts; mineral substances or ash in coal; transition metals and their oxides and salts; and eutectic salt mixtures. Studies involving the use of gasification catalysts have been conducted. However, most of the studies focused on the application of individual catalysts. Only two publications have reported the study of gasification of coal char in CO2 and steam catalyzed by eutectic salt mixture catalysts. By using the eutectic mixtures of salts that show good activity as individual compounds, the gasification temperature can be reduced possibly with still better activity and gasification rates due to improved dispersion of the molten catalyst on the coal particles. For similar metal/carbon atomic ratios, eutectic catalysts were found to be consistently more active than their respective single salts. But the exact roles that the eutectic salt mixtures play in these are not well understood and details of the mechanisms remain unclear. The effects of the surface property of coals and the application methods of eutectic salt mixture catalysts with coal chars on the reactivity of gasification will be studied. Based on our preliminary evaluation of the literature, a ternary

Eu doped BaCl2/LiF eutectics were grown by the micro-pulling down method and their directionally solidified eutectic (DSE) system has been investigated. The grown eutectic showed main phases of cubic LiF and orthorhombic BaCl2. In these eutectics, the 399 nm emission of Eu2+ 4f5d was obtained. It shows the intrinsic decay time of about 410 ns. The light yield of the 1-mm-thick eutectic showed 7000 ph/5.5 MeV alpha-ray.

The use of gold based thin film multilayer systems for forming eutectic bonds on wafer scale is investigated and preliminary results will be presented. On polished 4 inch wafers different multilayer systems are developed using thin film techniques and bonded afterwards under reactive atmospheres and different bonding temperatures and forces. Pull tests are performed to extract the bonding strengths.

These 250 abstracts from the international literature provide summaries of the preparation, treatments, composition and structure, and properties of eutectic alloys. Techniques for directional solidification and treatments including glazing, coating, and fiber reinforcement are discussed. In addition to the mechanical and thermal properties, the superconducting, corrosion, resistance, and thermionic emission and adsorption properties are described.

The present paper describes and discusses the devitrification and crystallization process of wollastonite-tricalcium phosphate (W-TCP) eutectic glass. This process was studied in situ from room temperature up to 1375 degrees C, by neutron diffractometry in vacuum. The data obtained were combined and compared with those performed in ambient atmosphere by differential thermal analysis and with those of samples fired in air at selected temperatures, and then cooled down and subsequently studied by laboratory XRD and field emission scanning electron microscopy fitted with energy X-ray dispersive spectroscopy. The experimental evidence indicates that the devitrification of W-TCP eutectic glass begins at approximately 870 degrees C with the crystallization of a Ca-deficient apatite phase, followed by wollastonite-2M (CaSiO(3)) crystallization at approximately 1006 degrees C. At 1375 degrees C, the bio-glass-ceramic is composed of quasi-rounded colonies formed by a homogeneous mixture of pseudowollastonite (CaSiO(3)) and alpha-tricalcium phosphate (Ca(3)(PO(4))(2)). This microstructure corresponds to irregular eutectic structures. It was also found that it is possible to obtain from the eutectic composition of the wollastonite-tricalcium phosphate binary system a wide range of bio-glass-ceramics, with different crystalline phases present, through appropriate design of thermal treatments. PMID:19427932

Current trends toward miniaturization and the use of lead(Pb)-free solder in electronic packaging present new problems in the reliability of solder joints. This study was performed in order to understand the microstructure and microstructural evolution of small volumes of nominally eutectic Au-Sn solder joints (80Au-20Sn by weight), which gives insight into properties and reliability.

The Ni-Ni3Ta eutectic and a nickel-base alloy containing 30 wt pct Ta were solidified unidirectionally in an electron beam floating zone melting apparatus. It was found that the volume fraction of the Ni3Ta phase in the Ni-Ni3Ta eutectic mixture was increased from 7.6 to 36 volume pct in agreement with the theory as predicted. Tensile properties of the randomly solidified and unidirectionally solidified Ni-Ni3Ta eutectic were determined as function of solidification rate and temperature. It was found that the ultimate tensile strength decreased as both the test temperature and solidification rate increased. An elongation of 40 pct was obtained for a nickelbase alloy containing 30 wt at room temperature. This unusually large elongation was attributed to the superplastic behavior of the alloy. The critical currents versus the external fields at 2.5, 3.0, 3.5 and 4.2 deg for the unidirectionally solidified Pb-Sn eutectic were measured. The values of critical fields at zero critical currents were obtained by extrapolation.

One percent agar (% wt) was dissolved in the deep eutectic solvent (DES), (2-hydroxyethyl) trimethylammonium chloride/urea at a 1:2 molar ratio, and successfully electrospun into nanofibers. An existing electrospinning set-up, operated at 50 deg C, was adapted for use with an ethanol bath to collect...

Solvent penetration experiments and small-angle X-ray scattering reveal that phospholipids dissolved in a deep eutectic solvent (DES) spontaneously self-assemble into vesicles above the lipid chain melting temperature. This means DESs are one of the few nonaqueous solvents that mediate amphiphile self-assembly, joining a select set of H-bonding molecular solvents and ionic liquids. PMID:26701210

This grant began in June of 1996. Its long term goal is to be able to control the microstructure of directionally solidified eutectic alloys, through an improved understanding of the influence of convection. The primary objective of the present projects is to test hypotheses for the reported influence of microgravity on the microstructure of three fibrous eutectics (MnBi-Bi, InSb-NiSb, Al3Ni-Al). A secondary objective is to determine the influence of convection on the microstructure of other eutectic alloys. Two doctoral students and a masters student supported as a teaching assistant were recruited for this research. Techniques were developed for directional solidification of MnBi-Bi eutectics with periodic application of current pulses to produce an oscillatory freezing rate. Image analysis techniques were developed to obtain the variation in MnBi fiber spacing, which was found to be normally distributed. The mean and standard deviation of fiber spacing were obtained for several freezing conditions. Eighteen ampoules were prepared for use in the gradient freeze furnace QUELD developed at Queen's University for use in microgravity. Nine of these ampoules will be solidified soon at Queen's in a ground-based model. We hope to solidify the other nine in the QUELD that is mounted on the Canadian Microgravity Isolation Mount on MIR. Techniques are being developed for directional solidification of the Al-Si eutectic at different freezing rates, with and without application of accelerated crucible rotation to induce convection. For the first time, theoretical methods are being developed to analyze eutectic solidification with an oscillatory freezing rate. In a classical sharp-interface model, we found that an oscillatory freezing rate increases the deviation of the average interfacial composition from the eutectic, and increases the undercooling of the two phases by different amounts. This would be expected to change the volume fraction solidifying and the fiber spacing

A new method of ceramic-metal bonding using a transient gas-metal eutectic liquid is proposed, confirmed, and investigated using nickel/copper-oxygen/alumina as a model system. A low temperature gas-metal eutectic melt may be made transient (by solidification) through interaction with a more refractory metal component providing a ceramic-metal bond with good wetting, high strength, a broad process window (relative to conventional gas-metal eutectic bonds), high thermal stability, and controlled thermoelastic stress; transport of a more active species to the ceramic interface may further improve adherence. A eutectic between the low-melting component (copper) and a gas (oxygen) forms at the interface between the refractory metal (nickel) and ceramic (alumina). This interfacial liquid wets the surfaces and promotes bonding. Because the entire copper interlayer is melted, the processing window is wider than conventional gas-metal eutectic in terms of temperature, atmosphere, and time. The liquid (Cu-O) dissolves the active, refractory component (Ni) providing transport to the interface where a refractory bond phase (NiAl2O4) forms. Interactions at temperature consume the liquid phase causing isothermal solidification. Diffusional homogenization further increases the solidus temperature of the joint. Multilayer bond structures were produced using both foils and plating. Oxygen additions were investigated using pre-oxidation of each metal and/or oxidation in-situ. The best bonds resulted from foils combining nickel pre-oxidation with a eutectic atmosphere. The oxide layer slows the oxidation kinetics of the nickel which allows eutectic liquid to form providing wetting, reaction, and adherence to the ceramic. The interfacial bond structure consists of a uniform, thin (sub-micron) reaction layer of nickel-aluminate (NiAl2 O4) spinel. Adhesion is comparable to current technologies and can exceed the ceramic strength. Typical peel failure occurs at the metal

The UC2-x - carbon eutectic has been studied by laser heating and fast multi-wavelength pyrometry under inert atmosphere. The study has been carried out on three compositions, two of which close to the phase boundary of the UC2-x - C miscibility gap (with C/U atomic ratios 2 and 2.1), and one, more crucial, with a large excess of carbon (C/U = 2.82). The first two compositions were synthesised by arc-melting. This synthesis method could not be applied to the last composition, which was therefore completed directly by laser irradiation. The U - C - O composition of the samples was checked by using a combustion method in an ELTRA® analyser. The eutectic temperature, established to be 2737 K ± 20 K, was used as a radiance reference together with the cubic - tetragonal (α → β) solid state transition, fixed at 2050 K ± 20 K. The normal spectral emissivity of the carbon-richer compounds increases up to 0.7, whereas the value 0.53 was established for pure hypostoichiometric uranium dicarbide at the limit of the eutectic region. This increase is analysed in the light of the demixing of excess carbon, and used for the determination of the liquidus temperature (3220 K ± 50 K for UC2.82). Due to fast solid state diffusion, also fostered by the cubic - tetragonal transition, no obvious signs of a lamellar eutectic structure could be observed after quenching to room temperature. The eutectic surface C/UC2-x composition could be qualitatively, but consistently, followed during the cooling process with the help of the recorded radiance spectra. Whereas the external liquid surface is almost entirely constituted by uranium dicarbide, it gets rapidly enriched in demixed carbon upon freezing. Demixed carbon seems to quickly migrate towards the inner bulk during further cooling. At the α → β transition, uranium dicarbide covers again the almost entire external surface.

Laser remelting has been performed on Ni-30 wt.% Sn hypoeutectic alloy. An anomalous eutectic formed at the bottom of the molten pool when the sample was remelted thoroughly. 3D morphologies of the α-Ni and Ni3Sn phases in the anomalous eutectic region were obtained and investigated using serial sectioning reconstruction technology. It is found that the Ni3Sn phase has a continuous interconnected network structure and the α-Ni phase is distributed as separate particles in the anomalous eutectic, which is consistent with the electron backscatter diffraction pattern examinations. The α-Ni particles in the anomalous eutectic are supersaturated with Sn element as compared with the equilibrium phase diagram. Meanwhile, small wavy lamella eutectics coexist with anomalous eutectics. The Trivedi-Magnin-Kurz model was used to estimate undercooling with lamellar spacing. The results suggest that the critical undercooling found in undercooling solidification is not a sufficient condition for anomalous eutectic formation. Besides, α-Ni particles in the anomalous eutectic do not exhibit a completely random misorientation and some neighboring α-Ni particles have the same orientation. It is shown that both the coupled and decoupled growth of the eutectic two phases can generate the α-Ni + Ni3Sn anomalous eutectic structure.

An apparatus and method for continuous production of liquid uranium alloys through the electrolytic reduction of uranium chlorides. The apparatus includes an electrochemical cell formed from an anode shaped to form an electrolyte reservoir, a cathode comprising a metal, such as iron, capable of forming a eutectic uranium alloy having a melting point less than the melting point of pure uranium, and molten electrolyte in the reservoir comprising a chlorine or fluorine containing salt and uranium chloride. The method of the invention produces an eutectic uranium alloy by creating an electrolyte reservoir defined by a container comprising an anode, placing an electrolyte in the reservoir, the electrolyte comprising a chlorine or fluorine containing salt and uranium chloride in molten form, positioning a cathode in the reservoir where the cathode comprises a metal capable of forming an uranium alloy having a melting point less than the melting point of pure uranium, and applying a current between the cathode and the anode.

Resolution of microscopic analytical methods has greatly improved over the past decade, and it is now possible to examine periodic variations in structure and chemistry at a scale much finer than the spacing typical of eutectic structures (1-5 [mu]m). During the current year, studies were completed on ZrO[sub 2]-NiO and ZrO[sub 2]-MnO eutectic systems, and study was initiated on microchemical variation in two spinodal systems: Cu-Ni-Sn and SnO[sub 2]-TiO[sub 2]. Work was also initiated on metal/oxide interface microchemistry, in particular the corrosion interface resulting during oxidation of Cu-Sn alloys. 6 figs.

We study the electromagnetic (EM) response of anisotropic eutectic metamaterials, consisting in cylindrical polaritonic LiF rods embedded in a KCl host. The specular reflectance of the samples was measured at far infrared (3-12 THz). The sample reflection was simulated by modeling the eutectic structure and solving numerically Maxwell equations for the EM fields. The reflectance was also calculated from simple effective response functions models. A good agreement was obtained between experimental and calculated spectra. From the effective response functions calculations, we obtained a range of frequencies in which the system behaves as a homogeneous effective anisotropic media, with a hyperbolic dispersion relation, opening possibilities for negative refraction and focusing applications.

Chemical ordering at metastable eutectics was recognized in non-equilibrium gas-to- solid condensation experiments to constrain 'silicate' dust formation in O-rich circumstellar environments. The predictable metastable eutectic behavior successfully predicted the observed ferromagnesiosilica, compositions of circumstellar dust, presolar and solar nebula grains in the matrix of the collected aggregate IDPs. Many of the experimentally determined metastable eutectic solids match the fundamental building blocks of common rock-forming layer silicates: this could have implications for the origin of Life. The physical conditions conducive to metastable eutectic behavior, i.e. high temperature and (ultra)fast quenching, lead to unique amorphous, typically nano- to micrometer-sized, materials. The new paradigm of metastable eutectic behavior opens the door to new and exciting research opportunities in uncovering the many implications of these unique amorphous and typically nano- to micrometer-sized, metastable eutectic materials.

Chemical ordering at metastable eutectics was recognized in non-equilibrium gas-to- solid condensation experiments to constrain 'silicate' dust formation in O-rich circumstellar environments. The predictable metastable eutectic behavior successfully predicted the observed ferromagnesiosilica compositions of circumstellar dust presolar and solar nebula grains in the matrix of the collected aggregate IDPs (Interplanetary Dust Particles). Many of the experimentally determined metastable eutectic solids match the fundamental building blocks of common rock-forming layer silicates: this could have implications for the origin of Life. The physical conditions conducive to metastable eutectic behavior, i.e. high temperature and (ultra) fast quenching, lead to unique amorphous, typically nano- to micrometer-sized, materials. The new paradigm of metastable eutectic behavior opens the door to new and exciting research opportunities in uncovering the many implications of these unique amorphous, and typically nano-to micrometer-sized, metastable eutectic materials.

A research program is in progress at Rocky Flats to determine correlations between ultrasonic signal content and diffusion or eutectic bond joint condition, and to develop a computer-controlled scanning, data acquisition and analysis system which utilizes these correlations and waveform analysis techniques. The initial efforts to determine effective ultrasonic waveform parameters to characterize the strength of bond interfaces is complete. A development version of a computer-controlled, automated scanning and data acquisition system is in operation.

In alloys, solidification takes place along various paths which may be ascertained via phase diagrams; while there would be no single formula applicable to all alloys, an approximate formula for a specific solidification path would be useful in estimating the fraction of the solid formed during recalescence. A formulation is here presented of recalescence in binary eutectic alloys. This formula is applied to Ag-Cu alloys which are of interest in containerless solidification, due to their formation of supersaturated solutions.

By suitable control of thermal conditions in directional-solidification process, supperalloy structural and machine components (e.g., turbine blades) cast with microstructures enhancing resistance to fatigue. Specific version of process and thermal conditions chosen to reduce micro-segregation during solidification and to minimize or eliminate script carbide and eutectic-phase inclusions, which are brittle inclusions found to decrease resistance to fatigue.

Mixtures of phenols/ketones and urea show eutectic behavior upon gentle heating. These mixtures possess liquid-crystalline-like phases that can be processed. The architecture of phenol/ketone acts as structure-donating motif, while urea serves as melting-point reduction agent. Condensation at elevated temperatures results in nitrogen-containing carbons with remarkably high nitrogen content of mainly pyrazinic nature. PMID:26178584

We present a statistical analysis of the first four seasons from a `second-generation' microlensing survey for extrasolar planets, consisting of near-continuous time coverage of 8 deg2 of the Galactic bulge by the Optical Gravitational Lens Experiment (OGLE), Microlensing Observations in Astrophysics (MOA), and Wise microlensing surveys. During this period, 224 microlensing events were observed by all three groups. Over 12 per cent of the events showed a deviation from single-lens microlensing, and for ˜one-third of those the anomaly is likely caused by a planetary companion. For each of the 224 events, we have performed numerical ray-tracing simulations to calculate the detection efficiency of possible companions as a function of companion-to-host mass ratio and separation. Accounting for the detection efficiency, we find that 55^{+34}_{-22} per cent of microlensed stars host a snowline planet. Moreover, we find that Neptune-mass planets are ˜10 times more common than Jupiter-mass planets. The companion-to-host mass-ratio distribution shows a deficit at q ˜ 10-2, separating the distribution into two companion populations, analogous to the stellar-companion and planet populations, seen in radial-velocity surveys around solar-like stars. Our survey, however, which probes mainly lower mass stars, suggests a minimum in the distribution in the super-Jupiter mass range, and a relatively high occurrence of brown-dwarf companions.

We present preliminary results on the eutectic bonding between two {100} Ge single crystal surfaces using thin films of Au ranging from 900Å/surface to 300Å/surface and Pd (10% the thickness of Au). Following bonding, plan view optical microscopy (OM) of the cleaved interface of samples with Au thicknesses ≤ 500Å/surface show a eutectic morphology more conducive to phonon transmission through the bond interface. High resolution transmission electron microscopy (HRTEM) cross sectional interface studies of a 300Å/surface Au sample show <100> epitaxial growth of Ge. In sections of the bond, lattice continuity of the Ge is apparent through the interface. TEM studies also reveal <110> heteroepitaxial growth of Au with a Au-Ge lattice mismatch of less than 2%. Eutectic bonds with 200Å/surface Au have been attained with characterization pending. An optical polishing technique for Ge has been optimized to insure intimate contact between the Ge surfaces prior to bonding. Interferometry analysis of the optically polished Ge surface shows that surface height fluctuations lie within ±150Å across an interval of 1mm. Characterization of phonon transmission through the interface is discussed with respect to low temperature detection of ballistic phonons.

The characteristics of the Al-Al3Ni eutectic structure are examined with emphasis on its morphology and crystallography. Based on these examinations, the mechanism of formation of this technologically important eutectic is postulated. It is found that a thin shell of α-Al forms coherently around each Al3Ni fiber. The excellent thermal stability of the Al-Al3Ni eutectic may be attributed to the presence of this coherent layer.

For the purpose of hardening steel with eutectic coatings, the corresponding composition of powders, pastes, daubings or solid metal element is fused directly on the surface of the part, or prepared eutectic alloys are applied to the surface to be hardened. The purpose of this study was an investigation of the features of the formation on steel of thick (more than 1mm) diffusion-fused eutectic coatings from powder mixtures.

An element comprising sapphire, ruby or blue sapphire can be bonded to another element of such material with a eutectic mixture of aluminum oxide and zirconium oxide. The bonding mixture may be applied in the form of a distilled water slurry or by electron beam vapor deposition. In one embodiment the eutectic is formed in situ by applying a layer of zirconium oxide and then heating the assembly to a temperature above the eutectic temperature and below the melting point of the material from which the elements are formed. The formation of a sapphire rubidium maser cell utilizing eutectic bonding is shown.

Bonding of an element comprising sapphire, ruby or blue sapphire to another element of such material with a eutectic mixture of aluminum oxide and zirconium oxide is discussed. The bonding mixture may be applied in the form of a distilled water slurry or by electron beam vapor deposition. In one embodiment the eutectic is formed in situ by applying a layer of zirconium oxide and then heating the assembly to a temperature above the eutectic temperature and below the melting point of the material from which the elements are formed. The formation of a sapphire rubidium maser cell utilizing eutectic bonding is shown.

The influences of high magnetic field (up to 12 T) on the morphology of Pb-Sn and Al-Al2Cu lamellar eutectics during directional solidification were investigated. The experimental results indicate that, along with a decrease in eutectic spacing, the banded structure forms at lower growth speeds under high magnetic field and the band spacing decreases as the magnetic field increases. Moreover, the application of a magnetic field enriches the Cu solute in the liquid ahead of the liquid/solid interface during directional solidification of an Al-Al2Cu eutectic alloy. The effects of high magnetic field on the eutectic points of non-ferromagnetic alloys and the stress acting on the eutectic lamellae during directional solidification have been studied. Both thermodynamic evaluation and DTA measurements reveal that the high magnetic field has a negligible effect on the eutectic points of non-ferromagnetic alloys. However, the high magnetic field caused an increase of the nucleation temperature and undercooling. The numerical results indicate that a considerable stress is produced on the eutectic lamellae during directional solidification under high magnetic field. The formation of a banded structure in a lamellar eutectic during directional solidification under high magnetic field may be attributed to both the buildup of the solute in the liquid ahead of the liquid/solid interface and the stress acting on the eutectic lamellae.

The outstading mechanical properties of bimodal ultrafine eutectic composites (BUECs) containing length scale hierarchy in eutectic structure were demonstrated by using AFM observation of surface topography with quantitative height measurements and were interpreted in light of the details of the deformation mechanisms by three different interface modes. It is possible to develop a novel strain accommodated eutectic structure for triggering three different interface-controlled deformation modes; (I) rotational boundary mode, (II) accumulated interface mode and (III) individual interface mode. A strain accommodated microstructure characterized by the surface topology gives a hint to design a novel ultrafine eutectic alloys with excellent mechanical properties. PMID:25265897

The influences of high magnetic field (up to 12 T) on the morphology of Pb-Sn and Al-Al2Cu lamellar eutectics during directional solidification were investigated. The experimental results indicate that, along with a decrease in eutectic spacing, the banded structure forms at lower growth speeds under high magnetic field and the band spacing decreases as the magnetic field increases. Moreover, the application of a magnetic field enriches the Cu solute in the liquid ahead of the liquid/solid interface during directional solidification of an Al-Al2Cu eutectic alloy. The effects of high magnetic field on the eutectic points of non-ferromagnetic alloys and the stress acting on the eutectic lamellae during directional solidification have been studied. Both thermodynamic evaluation and DTA measurements reveal that the high magnetic field has a negligible effect on the eutectic points of non-ferromagnetic alloys. However, the high magnetic field caused an increase of the nucleation temperature and undercooling. The numerical results indicate that a considerable stress is produced on the eutectic lamellae during directional solidification under high magnetic field. The formation of a banded structure in a lamellar eutectic during directional solidification under high magnetic field may be attributed to both the buildup of the solute in the liquid ahead of the liquid/solid interface and the stress acting on the eutectic lamellae.

It is well established that the lamellar eutectic structure exhibits a limited range of spacings rather than a unique spacing during steady state growth at a constant growth velocity. The minimum observed spacing corresponds to the extremum spacing predicted by the Jackson and Hunt analysis of eutectic growth. However, the maximum observed spacing is much less than the maximum spacing predicted by their analysis. The assumption of a planar interface by Jackson and Hunt is relaxed in this paper and a numerical model is developed which uses the boundary element method and an iterative technique to obtain the solute distribution for a selfconsistent curved interface shape. The maximum selfconsistent spacing, for which a selfconsistent interface exists, is determined for several growth velocities. The maximum selfconsistent spacings calculated in this way show good agreement with the maximum spacings observed in the CBr 4C 2Cl 6 eutectic system. The interface shape for the maximum selfconsistent spacings has a limiting slope which is far from vertical and the deepest point on the selfconsistent interface at the maximum spacing does not lie in a deep pocket.

We present an analysis of the anomalous microlensing event, MOA-2010-BLG-073, announced by the Microlensing Observations in Astrophysics survey on 2010 March 18. This event was remarkable because the source was previously known to be photometrically variable. Analyzing the pre-event source light curve, we demonstrate that it is an irregular variable over timescales >200 days. Its dereddened color, (V - I) {sub S,0}, is 1.221 {+-} 0.051 mag, and from our lens model we derive a source radius of 14.7 {+-} 1.3 R {sub Sun }, suggesting that it is a red giant star. We initially explored a number of purely microlensing models for the event but found a residual gradient in the data taken prior to and after the event. This is likely to be due to the variability of the source rather than part of the lensing event, so we incorporated a slope parameter in our model in order to derive the true parameters of the lensing system. We find that the lensing system has a mass ratio of q = 0.0654 {+-} 0.0006. The Einstein crossing time of the event, t {sub E} = 44.3 {+-} 0.1 days, was sufficiently long that the light curve exhibited parallax effects. In addition, the source trajectory relative to the large caustic structure allowed the orbital motion of the lens system to be detected. Combining the parallax with the Einstein radius, we were able to derive the distance to the lens, D{sub L} = 2.8 {+-} 0.4 kpc, and the masses of the lensing objects. The primary of the lens is an M-dwarf with M {sub L,1} = 0.16 {+-} 0.03 M {sub Sun }, while the companion has M {sub L,2} = 11.0 {+-} 2.0 M {sub J}, putting it in the boundary zone between planets and brown dwarfs.

We report the detection of the cool, Jovian-mass planet MOA-2007-BLG-400Lb. The planet was detected in a high-magnification microlensing event (with peak magnification A max = 628) in which the primary lens transited the source, resulting in a dramatic smoothing of the peak of the event. The angular extent of the region of perturbation due to the planet is significantly smaller than the angular size of the source, and as a result the planetary signature is also smoothed out by the finite source size. Thus, the deviation from a single-lens fit is broad and relatively weak (approximately few percent). Nevertheless, we demonstrate that the planetary nature of the deviation can be unambiguously ascertained from the gross features of the residuals, and detailed analysis yields a fairly precise planet/star mass ratio of q=(2.5^{+0.5}_{-0.3})× 10^{-3}}, in accord with the large significance (Δ χ^2=1070}) of the detection. The planet/star projected separation is subject to a strong close/wide degeneracy, leading to two indistinguishable solutions that differ in separation by a factor of ~8.5. Upper limits on flux from the lens constrain its mass to be M < 0.75 M sun (assuming that it is a main-sequence star). A Bayesian analysis that includes all available observational constraints indicates a primary in the Galactic bulge with a mass of ~0.2-0.5 M sun and thus a planet mass of ~0.5-1.3 M Jup. The separation and equilibrium temperature are ~5.3-9.7 AU (~0.6-1.1 AU) and ~34 K (~103 K) for the wide (close) solution. If the primary is a main-sequence star, follow-up observations would enable the detection of its light and so a measurement of its mass and distance.

Metal eutectic fluxes are useful for exploratory synthesis of new intermetallic phases. In this work the use of cerium/transition metal eutectics such as: Ce/Co, Ce/Ni, and Ce/Fe have yielded many new synthetically and magnetically complex phases. Structural units that were previously observed in phases grown in La/Ni eutectic reactions have also been observed in new structures and analogs grown from cerium/transition metal eutectics. These structural units include a main group element coordinated by 9 rare-earth atoms (such as the Al Ce9 clusters seen in Ce31.0(2)Fe11.8(5)Al6.5(6) B13C4), trigonal planar FeC3 units (also seen in Ce31.0(2)Fe11.8(5)Al6.5(6)B 13C4), iron clusters capped by light elements (Fe4C 6 frustrated tetrahedral in Ce21Fe8M7C 14, and larger Fe clusters in Ce33Fe14B25 C34). Variants of these building blocks were observed in Ce10Co2B7C16 with square Co units and chains of B and C connected to them, Fe2C8 units observed in Ce7Fe2C9, and FeC4 observed in Ce4FeGa0.85Al0.15C4 and Ce4FeAlC4. Two new phases were grown from Ce/Fe eutectic, Ce33Fe 14B25C34 and Ce33Fe13B 18C34 which exhibits very similar structures, but significantly different magnetic behavior. Structurally these two phases are similar. Both crystallize in the Im-3m space group, but differ by the centering of the Fe clusters. Ce33Fe14B25C34 contains Fe clusters centered by B atoms and Al doped on the Fe2 site. In Ce33Fe13B18C34, the Fe cluster is a perfect cuboctahedron. Ce33Fe14B25 C34 exhibits mixed valent behavior of cerium at 75K and no magnetic moment on iron, where-as Ce33Fe13B18C 34 exhibits tetravalent cerium and its iron clusters undergo a ferromagnetic transition at 180K. Another borocarbide, Ce10Co2B7C 16 was synthesized from Ce/Co eutectic flux. This structure features squares of Co surrounded by chains of C and B and a sea of cerium atoms. Temperature dependent magnetic susceptibility measurements at 1 Tesla were fit to a modified Curie-Weiss law and a moment per Ce was

The mechanisms of Al-Si eutectic refinement due to scandium (Sc) additions have been studied in an Al-7Si-0.3Mg foundry alloy. The evolution of eutectic microstructure is studied by thermal analysis and interrupted solidification, and the distribution of Sc is studied by synchrotron micro-XRF mapping. Sc is shown to cause significant refinement of the eutectic silicon. The results show that Sc additions strongly suppress the nucleation of eutectic silicon due to the formation of ScP instead of AlP. Sc additions change the macroscopic eutectic growth mode to the propagation of a defined eutectic front from the mold walls opposite to the heat flux direction similar to past work with Na, Ca, and Y additions. It is found that Sc segregates to the eutectic aluminum and AlSi2Sc2 phases and not to eutectic silicon, suggesting that impurity-induced twinning does not operate. The results suggest that Sc refinement is mostly caused by the significantly reduced silicon nucleation frequency and the resulting increase in mean interface growth rate.

We present simulations of the nucleation and equiaxed dendritic growth of the primary hexagonal close-packed -Mg phase followed by the nucleation of the -phase in interdendritic regions. A zoomed-in region of a melt channel under eutectic conditions is investigated and compared with experiments. The presented simulations allow prediction of the final properties of an alloy based on process parameters. The obtained results give insight into the solidification processes governing the microstructure formation of Mg-Al alloys, allowing their targeted design for different applications.

Pb-Sn eutectic alloy was directionally solidified at 1.4 to 3.2 cm/hr with forced convection induced by axial vibration of the growth ampoule with a frequency of 10 to 40 Hz and an amplitude of 0.5 to 1.0 mm. To determine the exact growth rate, an interface demarcation technique was applied. The lamellar spacing was increased 10 to 40 percent in ingots solidified with vibration compared to those solidified without vibration. The average intensity of convection in the melt under axial vibration of the ampoule was estimated by comparing the experimental results with a theoretical model.

The effect of melt supercooling on the microstructure of an Nb-58 at. pct Si alloy is investigated experimentally using an electromagnetic levitation apparatus. It is found that, starting with an alloy nominally of eutectic composition, nucleation of Nb5Si3 occurs in the supercooled liquid first. Upon further cooling, the remaining liquid continues to supercool until the second phase, NbSi2 is nucleated, which is commonly accompanied by rapid recalescence. The primary phase exibits a eutectoid-type decomposition. The observations are discussed with reference to the results of quantitative microstructural measurements, compositional and thermal analysis, and preliminary thermodynamic modeling of the phase diagram.

The paper discusses the peculiarities of a structure and a coating composition after reflow. It was established that the structure of coatings from nickel alloy is a solid solution based on nickel, the eutectic of γ-Ni+Ni3B composition and dispersed reinforcing particles. The content of alloying elements in the initial powder material determines the type of the coating structure and the formation of hypoeutectic or hypereutectic structures. The influence of formation conditions on the structure and physical-mechanical properties of the coatings is considered in this paper.

The suitability of the eutectics for high temperature fasteners was investigated. Material properties were determined as a function of temperature, and included shear parallel and perpendicular to the growth direction and torsion parallel to it. Techniques for fabricating typical fastener shapes included grinding, creep forming, and direct casting. Both lamellar Ni3Al-Ni3Nb and fibrous (Co,Cr,Al)-(Cr,Co)7C3 alloys showed promise as candidate materials for high temperature fastener applications. A brief evaluation of the performance of the best fabricated fastener design was made.

For the first time, the microstructure of directionally solidified ternary eutectics is visualized in three dimensions, using a high-resolution technique of X-ray tomography at the ESRF. The microstructure characterization is conducted with a photon energy, allowing to clearly discriminate the three phases Ag2Al, Al2Cu, and α-Aluminum solid solution. The reconstructed images illustrate the three-dimensional arrangement of the phases. The Ag2Al lamellae perform splitting and merging as well as nucleation and disappearing events during directional solidification.

Growth patterns during liquid/solid phase transformation are governed by simultaneous effects of heat and mass transfer mechanisms, creation of new interfaces, jump of the crystallization units from liquid to solid and their rearrangement in the solid matrix. To examine how the above processes influence the scale of microstructure, two eutectic systems are chosen for the study: a polymeric system polyethylene glycol-p-dibromobenzene (PEG-DBBZ) and a simple molecular system succinonitrile (SCN)-camphor. The scaling law for SCN-camphor system is found to follow the classical Jackson-Hunt model of circular rod eutectic, where the diffusion in the liquid and the interface energy are the main physics governing the two-phase pattern. In contrast, a significantly different scaling law is observed for the polymer system. The interface kinetics of PEG phase and its solute concentration dependence thus have been critically investigated for the first time by directional solidification technique. A model is then proposed that shows that the two-phase pattern in polymers is governed by the interface diffusion and the interface kinetics. In SCN-camphor system, a new branch of eutectic, elliptical shape rodl, is found in thin samples where only one layer of camphor rods is present. It is found that the orientation of the ellipse can change from the major axis in the direction of the thickness to the direction of the width as the velocity and/or the sample thickness is decreased. A theoretical model is developed that predicts the spacing and orientation of the elliptical rods in a thin sample. The single phase growth patterns of SCN-camphor system were also examined with emphasis on the three-dimensional single cell and cell/dendrite transition. For the 3D single cell in a capillary tube, the entire cell shape ahead of the eutectic front can be described by the Saffmann-Taylor finger only at extremely low growth rate. A 3D directional solidification model is developed to

Charge transport and structural dynamics in a series of imidazole and carboxylic acid-based deep eutectic mixtures are investigated by broadband dielectric spectroscopy, dynamic light scattering, 1H nuclear magnetic resonance spectroscopy, calorimetry, and Fourier transform infrared spectroscopy. It is found that the extended hydrogen-bonded networks characteristic of imidazoles are broken down upon addition of carboxylic acids, resulting in an increase in dc conductivity of the mixtures. These results are discussed within the framework of recent theories of hydrogen bonding and proton transport.

A directionally solidified NiAl-Mo eutectic and an NiAl intermetallic, having respective nominal compositions Ni-45.5Al-9Mo and Ni-45.2Al (at.%), were loaded in compression at 1073 and 1173 K. Formidable strengthening by regularly distributed Mo fibres (average diameter 600 nm, volume fraction 14%) was observed. The fibres can support compression stresses transferred from the plastically deforming matrix up to a critical stress of the order of 2.5 GPa, at which point they yield. Microstructural evidence is provided for the dislocation-mediated stress transfer from the NiAl to the Mo phase.

Deep eutectic solvents (DESs) were evaluated as solvents in centrifugal partition chromatography, a liquid-liquid chromatography separation technology. To this end, the partition coefficients of ten natural compounds of different hydrophobicity were determined in non-aqueous biphasic systems containing DES. The influence of the composition of DESs and the presence of water in the biphasic system on the partition coefficient were also examined. In addition, several process relevant physical properties of the biphasic system, such as the density and viscosity of the phases, were measured. A mixture of three to four hydrophobic compounds was successfully separated in a centrifugal partition extractor using a heptane/ethanol/DES biphasic system. PMID:26810802

This paper presents and investigates a novel technique for the footprint and thickness-independent selective release of Au-Si eutectically bonded microstructures through the localized removal of their eutectic bond interface. The technique is based on the electrochemical removal of the gold in the eutectic layer and the selectivity is provided by patterning the eutectic layer and by proper electrical connection or isolation of the areas to be etched or removed, respectively. The gold removal results in a porous silicon layer, acting similar to standard etch holes in a subsequent sacrificial release etching. The paper presents the principle and the design requirements of the technique. First test devices were fabricated and the method successfully demonstrated. Furthermore, the paper investigates the release mechanism and the effects of different gold layouts on both the eutectic bonding and the release procedure.

We developed eutectic solder bonding for the microelectromechanical systems (MEMS) probe card. We tested various eutectic solder materials, such as Sn, AgSn, and AuSn, and investigated the bonding ability of Sn-based multi-element alloys and their resistance to chemical solutions. The Sn-based alloys were formed by sputtering, electroplating, and the use of solder paste. According to our experimental results, Sn-rich solders, such as Ag3.5Sn, Ag3.5Sn96Cu0.5, and Sn, were severely damaged by silicon wet etchant such as potassium hydroxide (KOH) and tetramethylammonium hydroxide (TMAH). On the other hand Au80Sn20 was resistant to those chemicals. In order to verify the joint bondability of the solders, we used a cantilever probe beam, and bump which were made of nickel and nickel alloy. After flip-chip bonding of the cantilever beam and the bump with Au80Sn20 solder paste, we measured the contact force to verify the mechanical strength. We then re-inspected it with X-rays and found no voids in the joint.

The manner in which the eutectic cream EMLA enhances the percutaneous penetration of lidocaine and prilocaine into human skin is still not fully understood. The purpose of this study was to investigate if the modification of drug aggregation played a role in the way EMLA facilitates delivery. Light scattering analysis of lidocaine alone in water gave a critical aggregation concentration (CAC) of 572 μM and a mean aggregate size of 58.8 nm. The analysis of prilocaine in identical conditions gave a CAC of 1177 μM and a mean aggregate size of 105.7 ± 24.8 nm. When the two drugs were mixed at their eutectic 1:1 ratio in water the CAC reduced to 165.8 μM and the aggregate size was 43.82 nm. This lidocaine-prilocaine interaction in water was further modified upon addition of polyoxyethylene hydrogenated castor oil, the surfactant in the EMLA aqueous phase, to produce aggregates of <20 nm. The physical characterisation data suggested that it was the EMLA cream's surfactant that modified the drug molecular interactions in the aqueous continuous phase and caused a 6 fold higher drug penetration through human epidermal tissue compared to the oil formulations tested in this study. PMID:26732522

An apparatus and method are disclosed for continuous production of liquid uranium alloys through the electrolytic reduction of uranium chlorides. The apparatus includes an electrochemical cell formed from an anode shaped to form an electrolyte reservoir, a cathode comprising a metal, such as iron, capable of forming a eutectic uranium alloy having a melting point less than the melting point of pure uranium, and molten electrolyte in the reservoir comprising a chlorine or fluorine containing salt and uranium chloride. The method of the invention produces an eutectic uranium alloy by creating an electrolyte reservoir defined by a container comprising an anode, placing an electrolyte in the reservoir, the electrolyte comprising a chlorine or fluorine containing salt and uranium chloride in molten form, positioning a cathode in the reservoir where the cathode comprises a metal capable of forming an uranium alloy having a melting point less than the melting point of pure uranium, and applying a current between the cathode and the anode. 2 figures.

Extra-large-pore aluminophosphate -CLO (i.e., DNL-1) nanocrystals were synthesized in a eutectic mixture composed of diethylamine hydrochloride (DEAC) and ethylene glycol (EG) with 1-methylimidazole (1-MIm) as an additional amine using both conventional and microwave heating. The effects of the synthesis parameters, such as the amount of 1-MIm and the P/Al ratio, on the formation of DNL-1 nanocrystals were studied. The products were characterized using a variety of techniques. XRD, DLS, SEM and TEM results indicate that the as-synthesized DNL-1 nanocrystals have good crystallinity and narrow particle size distributions, and their average particle size was controlled in the 100-220nm range by simply adjusting the amount of 1-MIm. TG-DSC and N2 adsorption analyses reveal that the as-synthesized DNL-1 nanocrystals exhibit good thermal stability and the calcined samples possess high BET surface areas and large pore volumes. In addition, the cooperative structure-directing effects of 1-MIm and the eutectic mixture cation (DEA(+)) in the formation of DNL-1 nanocrystals were discussed. PMID:25897847

To better characterize the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the anthracene (1) + pyrene (2) system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at 404 K at x1 = 0.22. A model based on eutectic formation can be used to predict the enthalpy of fusion associated with the mixture. For mixtures that contain x1 < 0.90, the enthalpy of fusion is near that of pure pyrene. This and X-ray diffraction results indicate that mixtures of anthracene and pyrene have pyrene-like crystal structures and energetics until the composition nears that of pure anthracene. Solid-vapor equilibrium studies show that mixtures of anthracene and pyrene form solid azeotropes at x1 of 0.03 and 0.14. Additionally, mixtures at x1 = 0.99 sublime at the vapor pressure of pure anthracene, suggesting that anthracene behavior is not significantly influenced by x2 = 0.01 in the crystal structure. PMID:21116474

From macroscopic measurements of deep eutectic solvents such as glyceline (1:2 molar ratio of choline chloride to glycerol), the long-range translational diffusion of the larger cation (choline) is known to be slower compared to that of the smaller hydrogen bond donor (glycerol). However, when the diffusion dynamics are analyzed on the subnanometer length scale, we discover that the displacements associated with the localized diffusive motions are actually larger for choline. This counterintuitive diffusive behavior can be understood as follows. The localized diffusive motions confined in the transient cage of neighbor particles, which precede the cage-breaking long-range diffusion jumps, are moremore » spatially constrained for glycerol than for choline because of the stronger hydrogen bonds the former makes with chloride anions. The implications of differential localized mobility of the constituents should be especially important for applications where deep eutectic solvents are confined on the nanometer length scale and their long-range translational diffusion is strongly inhibited (e.g., within microporous media).« less

From macroscopic measurements of deep eutectic solvents such as glyceline (1:2 molar ratio of choline chloride to glycerol), the long-range translational diffusion of the larger cation (choline) is known to be slower compared to that of the smaller hydrogen bond donor (glycerol). However, when the diffusion dynamics are analyzed on the subnanometer length scale, we discover that the displacements associated with the localized diffusive motions are actually larger for choline. This counterintuitive diffusive behavior can be understood as follows. The localized diffusive motions confined in the transient cage of neighbor particles, which precede the cage-breaking long-range diffusion jumps, are more spatially constrained for glycerol than for choline because of the stronger hydrogen bonds the former makes with chloride anions. The implications of differential localized mobility of the constituents should be especially important for applications where deep eutectic solvents are confined on the nanometer length scale and their long-range translational diffusion is strongly inhibited (e.g., within microporous media).

New trends in analytical chemistry encourage the development of smart techniques and methods aligned with Green Chemistry. In this sense, Natural Deep Eutectic Solvents represents an excellent opportunity as a new generation of green solvents. In this work a new application for them has been proposed and demonstrated. These solvents were synthesized by combinations of inexpensive and natural components like, Glucose, Fructose, Citric acid and Lactic acid. The different natural solvents were easily prepared and added to buffer solution in different concentrations, allowing the enhancement of electrochemical detection of an important representative antioxidant like quercetin (QR) with improved signal up to 380%. QR is a ubiquitous flavonoid widespread in plants and food of plant origin. The proposed method using phosphate buffer with a eutectic mixture of Citric acid, Glucose and water in combination with carbon screen printed electrodes exhibited a good analytical performance. Detection and quantification limits were of 7.97 and 26.3 nM respectively; and repeatability with %RSDs of 1.41 and 7.49 for peak potential and intensity respectively. In addition, it has proved to be faster, greener and cheaper than other sensors and chromatographic methods available with the additional advantage of being completely portable. Furthermore, the obtained results demonstrated that the proposed method is able for the determination of QR in complex food samples. PMID:27566343

We propose a model of equiaxed eutectic solidification that couples the macroscopic level of heat diffusion with the microscopic level of nucleation and growth of the eutectic grains. The heat equation with the source term corresponding to the latent heat release due to solidification is calculated numerically by means of an implicit finite difference method. In the time stepping scheme, the evolution of solid fraction is deduced from a stochastic model of nucleation and growth which uses the local temperature (interpolated from the FDM mesh) to determine the local grain density and the local growth rate. The solid-liquid interface of each grain is tracked by using a subdivision of each grain perimeter in a large number of sectors. The state of each sector (i.e. whether it is still in contact with the liquid or already captured by an other grain) and the increase of radius of each grain during one time step allows one to compute the increase of solid fraction. As for deterministic models, the results of the model are the evolution of temperature and of solid fraction at any point of the sample. Moreover the model provides a complete picture of the microstructure, thus not limiting the microstructural information to the average grain density but allowing one to compute any stereological value of interest. We apply the model to the solidification of gray cast iron.

From macroscopic measurements of deep eutectic solvents such as glyceline (1:2 molar ratio of choline chloride to glycerol), the long-range translational diffusion of the larger cation (choline) is known to be slower compared to that of the smaller hydrogen bond donor (glycerol). However, when the diffusion dynamics are analyzed on the subnanometer length scale, we find that the displacements associated with the localized diffusive motions are actually larger for choline. This counterintuitive diffusive behavior can be understood as follows. The localized diffusive motions confined in the transient cage of neighbor particles, which precede the cage-breaking long-range diffusion jumps, are more spatially constrained for glycerol than for choline because of the stronger hydrogen bonds the former makes with chloride anions. The implications of such differential localized mobility of the constituents should be especially important for applications where deep eutectic solvents are confined on the nanometer length scale and their long-range translational diffusion is strongly inhibited (e.g., within microporous media). PMID:26267182

Microlensing provides a unique tool to break the stellar to dark matter degeneracy in the inner Milky Way. We combine N-body dynamical models fitted to the Milky Way's Boxy/Peanut bulge with exponential disk models outside this, and compute the microlensing properties. Considering the range of models consistent with the revised MOA-II data, we find low dark matter fractions in the inner Galaxy: at the peak of their stellar rotation curve a fraction fv = (0.88 ± 0.07) of the circular velocity is baryonic (at 1σ, fv > 0.72 at 2σ). These results are in agreement with constraints from the EROS-II microlensing survey of brighter resolved stars, where we find fv = (0.9 ± 0.1) at 1σ. Our fiducial model of a disk with scale length 2.6 kpc, and a bulge with a low dark matter fraction of 12%, agrees with both the revised MOA-II and EROS-II microlensing data. The required baryonic fractions, and the resultant low contribution from dark matter, are consistent with the NFW profiles produced by dissipationless cosmological simulations in Milky Way mass galaxies. They are also consistent with recent prescriptions for the mild adiabatic contraction of Milky Way mass haloes without the need for strong feedback, but there is some tension with recent measurements of the local dark matter density. Microlensing optical depths from the larger OGLE-III sample could improve these constraints further when available.

The extinct moa of New Zealand included three families (Megalapterygidae; Dinornithidae; Emeidae) of flightless palaeognath bird, ranging in mass from <15 kg to >200 kg. They are perceived to have evolved extremely robust leg bones, yet current estimates of body mass have very wide confidence intervals. Without reliable estimators of mass, the extent to which dinornithid and emeid hindlimbs were more robust than modern species remains unclear. Using the convex hull volumetric-based method on CT-scanned skeletons, we estimate the mass of a female Dinornis robustus (Dinornithidae) at 196 kg (range 155–245 kg) and of a female Pachyornis australis (Emeidae) as 50 kg (range 33–68 kg). Finite element analysis of CT-scanned femora and tibiotarsi of two moa and six species of modern palaeognath showed that P. australis experienced the lowest values for stress under all loading conditions, confirming it to be highly robust. In contrast, stress values in the femur of D. robustus were similar to those of modern flightless birds, whereas the tibiotarsus experienced the highest level of stress of any palaeognath. We consider that these two families of Dinornithiformes diverged in their biomechanical responses to selection for robustness and mobility, and exaggerated hindlimb strength was not the only successful evolutionary pathway. PMID:24367537

We present the discovery of the first Neptune analog exoplanet or super-Earth with a Neptune-like orbit, MOA- 2013-BLG-605Lb. This planet has a mass similar to that of Neptune or a super-Earth and it orbits at 9 approximately 14 times the expected position of the snow line, a(sub snow), which is similar to Neptune's separation of 11 a(sub snow) from the Sun. The planet/host-star mass ratio is q = (3.6 +/- 0.7) × 10(exp -4) and the projected separation normalized by the Einstein radius is s = 2.39 +/- 0.05. There are three degenerate physical solutions and two of these are due to a new type of degeneracy in the microlensing parallax parameters, which we designate "the wide degeneracy." The three models have (i) a Neptune-mass planet with a mass of M(sub p) = 21(+6/-7)(M) orbiting a low-mass M-dwarf with a mass of M(sub h) = 0.19(+0.05/-0.06 (solar mass)), (ii) a mini-Neptune with M(sub p) = 7.9(+1.8/-1.5)(M)) orbiting a brown dwarf host with M(sub h) = 0.068(+0.019/-0.011(solar mass)), and (iii) a super-Earth with M(sub p) = 3.2(+0.5/-0.3(M)) orbiting a low-mass brown dwarf host with M(sub h) = 0.025(+0.005/-0.004)(solar mass)), which is slightly favored. The 3D planet-host separations are 4.6(+4.7/-1.2)au, 2.1(+1.0/-0.2)au, and 0.94(+0.67/-0.02)au, which are 8.9(+10.5/-1.4)m 12(+7/-1), or 14(+11/-1) times larger than a(sub snow) for these models, respectively. Keck adaptive optics observations confirm that the lens is faint. This discovery suggests that low-mass planets with Neptune-like orbits are common. Therefore processes similar to the one that formed Neptune in our own solar system or cold super-Earths may be common in other solar systems.

We present the discovery of the first Neptune analog exoplanet or super-Earth with a Neptune-like orbit, MOA-2013-BLG-605Lb. This planet has a mass similar to that of Neptune or a super-Earth and it orbits at 9 ∼ 14 times the expected position of the snow line, a snow, which is similar to Neptune's separation of 11 a snow from the Sun. The planet/host-star mass ratio is q = (3.6 ± 0.7) × 10‑4 and the projected separation normalized by the Einstein radius is s = 2.39 ± 0.05. There are three degenerate physical solutions and two of these are due to a new type of degeneracy in the microlensing parallax parameters, which we designate “the wide degeneracy.” The three models have (i) a Neptune-mass planet with a mass of {M}{{p}}={21}-7+6{M}\\oplus orbiting a low-mass M-dwarf with a mass of {M}{{h}}={0.19}-0.06+0.05{M}ȯ , (ii) a mini-Neptune with {M}{{p}}={7.9}-1.2+1.8{M}\\oplus orbiting a brown dwarf host with {M}{{h}}={0.068}-0.011+0.019{M}ȯ , and (iii) a super-Earth with {M}{{p}}={3.2}-0.3+0.5{M}\\oplus orbiting a low-mass brown dwarf host with {M}{{h}}={0.025}-0.004+0.005{M}ȯ , which is slightly favored. The 3D planet–host separations are {4.6}-1.2+4.7 au, {2.1}-0.2+1.0 au, and {0.94}-0.02+0.67 au, which are {8.9}-1.4+10.5, {12}-1+7, or {14}-1+11 times larger than a snow for these models, respectively. Keck adaptive optics observations confirm that the lens is faint. This discovery suggests that low-mass planets with Neptune-like orbits are common. Therefore processes similar to the one that formed Neptune in our own solar system or cold super-Earths may be common in other solar systems.

We present the discovery of the first Neptune analog exoplanet or super-Earth with a Neptune-like orbit, MOA-2013-BLG-605Lb. This planet has a mass similar to that of Neptune or a super-Earth and it orbits at 9 ˜ 14 times the expected position of the snow line, a snow, which is similar to Neptune's separation of 11 a snow from the Sun. The planet/host-star mass ratio is q = (3.6 ± 0.7) × 10‑4 and the projected separation normalized by the Einstein radius is s = 2.39 ± 0.05. There are three degenerate physical solutions and two of these are due to a new type of degeneracy in the microlensing parallax parameters, which we designate “the wide degeneracy.” The three models have (i) a Neptune-mass planet with a mass of {M}{{p}}={21}-7+6{M}\\oplus orbiting a low-mass M-dwarf with a mass of {M}{{h}}={0.19}-0.06+0.05{M}ȯ , (ii) a mini-Neptune with {M}{{p}}={7.9}-1.2+1.8{M}\\oplus orbiting a brown dwarf host with {M}{{h}}={0.068}-0.011+0.019{M}ȯ , and (iii) a super-Earth with {M}{{p}}={3.2}-0.3+0.5{M}\\oplus orbiting a low-mass brown dwarf host with {M}{{h}}={0.025}-0.004+0.005{M}ȯ , which is slightly favored. The 3D planet–host separations are {4.6}-1.2+4.7 au, {2.1}-0.2+1.0 au, and {0.94}-0.02+0.67 au, which are {8.9}-1.4+10.5, {12}-1+7, or {14}-1+11 times larger than a snow for these models, respectively. Keck adaptive optics observations confirm that the lens is faint. This discovery suggests that low-mass planets with Neptune-like orbits are common. Therefore processes similar to the one that formed Neptune in our own solar system or cold super-Earths may be common in other solar systems.

A comparative study of rapid solidification of Ag-Cu eutectic alloy processed via melt fluxing and drop-tube techniques is presented. A computational model is used to estimate the cooling rate and undercooling of the free fall droplets as this cannot be determined directly. SEM micrographs show that both materials consist of lamellar and anomalous eutectic structures. However, below the critical undercooling the morphologies of each are different in respect of the distribution and volume of anomalous eutectic. The anomalous eutectic in flux- undercooled samples preferentially forms at cell boundaries around the lamellar eutectic in the cell body. In drop-tube processed samples it tends to distribute randomly inside the droplets and at much smaller volume fractions. That the formation of the anomalous eutectic can, at least in part, be suppressed in the drop-tube is strongly suggestive that the formation of anomalous eutectic occurs via remelting process, which is suppressed by rapid cooling during solidification.

The eutectic alloys have a wide spectrum of applications due to their good castability and physical and mechanical properties. The interphase spacing resulting during solidification is an important microstructural feature that significantly influences the mechanical behavior of the material. Thus, knowledge of the evolution of the interphase spacing during solidification is necessary in order to properly design the solidification process and optimize the material properties. While the growth of regular eutectics is rather well understood, the irregular eutectics such as Al-Si or Fe-graphite exhibit undercoolings and lamellar spacings much larger than those theoretically predicted. Despite of a considerable amount of experimental and theoretical work a clear understanding of the true mechanism underlying the spacing selection in irregular eutectics is yet to be achieved. A new experimental study of the solidification of the eutectic Al-Si alloy will be reported in this paper. The measured interface undercoolings and lamellar spacing will be compared to those found in the literature in order to get more general information regarding the growth mechanism of irregular eutectics. A modification of the present theory of the eutectic growth is also proposed. The results of the modified mathematical model, accounting for a non-isothermal solid/liquid interface, will be compared to the experimental measurements.

Al-Si eutectic growth has been studied in-situ for the first time using X-ray video microscopy during directional solidification (DS) in unmodified and Sr-modified Al-Si-Cu alloys. In the unmodified alloys, Si is found to grow predominantly with needle-like tip morphologies, leading a highly irregular progressing eutectic interface with subsequent nucleation and growth of Al from the Si surfaces. In the Sr-modified alloys, the eutectic reaction is strongly suppressed, occurring with low nucleation frequency at undercoolings in the range 10 K to 18 K. In order to transport Cu rejected at the eutectic front back into the melt, the modified eutectic colonies attain meso-scale interface perturbations that eventually evolve into equiaxed composite-structure cells. The eutectic front also attains short-range microscale interface perturbations consistent with the characteristics of a fibrous Si growth. Evidence was found in support of Si nucleation occurring on potent particles suspended in the melt. Yet, both with Sr-modified and unmodified alloys, Si precipitation alone was not sufficient to facilitate the eutectic reaction, which apparently required additional undercooling for Al to form at the Si-particle interfaces.

Using different experimental techniques, microstructure, electrical resistivity, attenuation coefficient, and mechanical and thermal properties of the quenched Bi-Pb-Sn ternary eutectic alloy have been investigated. From the X-ray analysis, Bi3Pb7 and Bi-Sn meta-stable phases are detected, in addition to rhombohedral bismuth and Sn body-centered tetragonal phases. This study also compared the physical properties of the Bi-Sn-Pb ternary eutectic alloys with the base binary Bi-Sn and Bi-Pb eutectic alloys.

Transparent polymers with low glass transition temperatures are flexible materials and can serve as an optical waveguide or as substrates for the layer structure in applications such as humidity or temperature sensors. The background of this publication is the development of a laser-based process to bond silicon chips, which serve as emitter or detector in an optical system, on a substrate, without exposing the substrate to thermo-mechanical stress. Using transmission laser bonding of low-melting eutectic alloys, the necessary energy can be coupled into the fusion zone precisely to reduce the process time. In this paper, Si-chips with 52In48Sn and 66In34Bi layers are investigated to bond on rigid substrates. Experimental results are presented, which illustrate the mechanical stability of these compounds.

A process of eutectic wetting and bonding of contact preforms is described which can serve as weld points for interconnection of solar cells. The procedure obviates the need for welding too close to the shallow diffused junction of a solar cell and therefore minimizes mechanical or electrical degradation that is likely when welding directly to the cell metallization. In addition, control of welding parameters is simplified because the weld interconnection is now made to a relatively thick metal preform which is firmly attached to the solar cell. Gold clad kovar was used in this preliminary study. Bond strength was excellent and survived temperature cycling to liquid nitrogen temperature. Electrical performance degradation after alloying was erratic and varied from little or no degradation to severe shunting. The reasons for the loss in fill-factor which is frequently encountered with the present process and choice of materials are not clear at this time. Possible explanations and recommendations for future work are discussed.

Liquid lead-bismuth (Pb-Bi) eutectic (LBE) may see extensive use as a coolant fluid, and perhaps also as a spallation target, in next generation nuclear energy systems. While it is not as reactive as alkali metal liquids, it does present a long term corrosion problem with some materials, notably stainless steels. Mitigation of the corrosion problem may be achieved by producing and maintaining a protective oxide on exposed surfaces, through control of the concentration of dissolved oxygen in the LBE. We have developed an oxygen sensor based on available zirconia-based solid electrolytes used in the automotive industry, which represents a relatively inexpensive source of reproducible and reliable components. We will present the design considerations and characteristics of our sensor unit, and describe its use in the LBE test loop at Los Alamos for measurement and control of dissolved oxygen concentration.

The equilibrium evaporation of mercury from dilute solutions in liquid lead-bismuth eutectic (LBE) was studied in argon atmosphere. Mercury present as impurity in LBE was evaporated and detected by atomic fluorescence spectroscopy. A method which could accurately simulate the experimental data was developed. Coefficients of the Henry constant temperature correlation for mercury dissolved in LBE were determined. Experiments with samples from several different batches of LBE revealed that mercury at mole fractions between 10-6 and 10-12 and temperatures between 150 and 350 °C evaporated from liquid LBE close to ideal behavior. Evaporation of mercury from solid LBE on the other hand was unexpectedly high. These results are important for safety evaluations of LBE based spallation targets and accelerator driven systems.

The electrodeposition of zinc has been studied in two deep eutectic solvents. Unlike the metals studied to date in these liquids, zinc electrodeposition is not mass transport limited and the morphology of the deposit differs in the two liquids. This study shows that changing the concentration of solute affects the physical properties of the liquid to different extents although this is found to not effect the morphology of the metal deposited. EXAFS was used to show that the speciation of zinc was the same in both liquids. Double layer capacitance studies showed differences between the two liquids and these are proposed to be due to the adsorption of a species on the electrode which is thought to be chloride. The differences in zinc morphology is attributed to blocking of certain crystal faces leading to deposition of small platelet shaped crystals in the glycol based liquid. PMID:21519629

Pb-Sn eutectic alloy was directionally solidified at 1.4 to 3.2 cm/h with forced convection induced by axial vibration of the growth ampoule with a frequency of 10 to 40 Hz and an amplitude of 0.5 to 1.0 mm. To determine the exact growth rate, an interface demarcation technique was applied. The lamellar spacing was increased 10 to 40 percent in ingots solidified with vibration, compared to those solidified without vibration. The number of grain boundaries was increased by vibration. The average intensity of convection in the melt under axial vibration of the ampoule was estimated by comparing the experimental results with a theoretical model.

Ionic liquid (ILs) pretreatment of lignocellulosic biomass has attracted broad scientific interest, despite high costs, possible toxicity and energy intensive recycling. An alternative group of ionic solvents with similar physicochemical properties are deep eutectic solvents (DESs). Corncob residues were pretreated with three different DES systems: choline chloride and glycerol, choline chloride and imidazole, choline chloride and urea. The pretreated biomass was characterised in terms of lignin content, sugars concentration, enzymatic digestibility and crystallinity index. A reduction of lignin and hemicellulose content resulted in increased crystallinity of the pretreated biomass while the crystallinity of the cellulose fraction could be reduced, depending on DES system and operating conditions. The subsequent enzymatic saccharification was enhanced in terms of rate and extent. A total of 41 g fermentable sugars (27 g glucose and 14 g xylose) could be recovered from 100g corncob, representing 76% (86% and 63%) of the initially available carbohydrates. PMID:26005926

The thermodynamic properties of the liquid silumins (Al0.879Si0.121)1-xTrx, where Tr = Cu, Fe, Ni and Ti, have been measured, using the electromotive force method at 1040 K. It has been found that diluted solutions of Fe or Ni in eutectic silumins at Tr molar fractions of 0 < xFe ≤ 0.035 and 0 < xNi ≤ 0.027 are characterized by positive deviations from ideality for aluminium. However, the deviations become negative at increasing of the Tr concentration. However, molten silumins doped by Ti and Cu show negative deviations from Raoult's law for aluminium at the studied concentrations. Thermodynamic activity of Al in the silumins decreases in the sequence of Fe→Ni→Cu→Ti for the dopants.

Silver is an important metal for electronic connectors, however, it is extremely soft and wear can be a significant issue. This paper describes how improved wear resistant silver coatings can be obtained from the electrolytic deposition of silver from a solution of AgCl in an ethylene glycol/choline chloride based Deep Eutectic Solvent. An up to 10-fold decrease in the wear volume is observed by the incorporation of SiC or Al(2)O(3) particles. The work also addresses the fundamental aspect of speciation of silver chloride in solution using EXAFS to probe solution structure. The size but not the nature of the composite particles is seen to change the morphology and grain size of the silver deposit. Grain sizes are shown to be consistent with previous nucleation studies. The addition of LiF is found to significantly affect the deposit morphology and improve wear resistance. PMID:22249451

Electroplating of Fe films was carried out from choline chloride-ethylene glycol types of DES (Deep Eutectic Solvent). We investigated magnetic properties of the plated Fe films and evaluated the productivity for the electroplating process. Consequently, we found that surface morphology and current efficiency of the plated films were affected by the bath temperature. We obtained the Fe films with relatively smooth surface and high current efficiency in the bath temperature range from 70 to 110 °C. The deposition rate for our process depended on the current density, and we obtained high deposition rate value of approximately 120 μm/h. We also obtained high current efficiency values of approximately 90% in the wide range of plating time. These results indicate that the DES-based bath has industrial advantages for mass-producing Fe films. Therefore, we conclude that the DES-based bath is an attractive plating bath for Fe films.

National Measurement Institute of Australia (NMIA) has developed a miniature crucible design suitable for measurement by both thermocouples and radiation thermometry, and has established an ensemble of five Co-C eutectic-point cells based on this design. The cells in this ensemble have been individually calibrated using both ITS-90 radiation thermometry and thermocouples calibrated on the ITS-90 by the NMIA mini-coil methodology. The assigned ITS-90 temperatures obtained using these different techniques are both repeatable and consistent, despite the use of different furnaces and measurement conditions. The results demonstrate that, if individually calibrated, such cells can be practically used as part of a national traceability scheme for thermocouple calibration, providing a useful intermediate calibration point between Cu and Pd.

Interest in ordered porous structures has grown because of there unique properties such as photonic bandgaps, high backing packing density and high surface to volume ratio. Inspired by nature, biometric strategies using self assembled organic molecules dominate the development of hierarchical inorganic structures. Directional solidification of eutectics (DSE) also exhibit self assembly characteristics to form hierarchical metallic and inorganic structures. Crystallization of diphasic materials by DSE can produce two dimensional ordered structures consisting of rods or lamella. By selective removal of phases, DSE is capable to fabricate ordered pore arrays or ordered pin arrays. Criteria and limitations to fabricate hierarchical structures will be presented. Porous structures in silicon base alloys and ceramic systems will be reported.

The production of highly radiotoxic polonium isotopes poses serious safety concerns for the development of future nuclear systems cooled by lead bismuth eutectic (LBE). In this paper it is shown that polonium can be extracted efficiently from LBE using a mixture of alkaline metal hydroxides (NaOH + KOH) in a temperature range between 180 and 350 °C. The extraction ratio was analyzed for different temperatures, gas blankets and phase ratios. A strong dependence of the extraction performance on the redox properties of the cover gas was found. While hydrogen facilitates the removal of polonium, oxygen has a negative influence on the extraction. These findings open new possibilities to back up the safety of future LBE based nuclear facilities.

Some proposed advanced reactor concepts would be cooled by lead or lead-bismuth eutectic (LBE). An LBE test loop was designed and built at Los Alamos to develop the engineering and materials technology necessary to successfully implement LBE as a coolant (Fig. 1). Operational since December 2001, this test loop has been used to develop and demonstrate safe operation, oxygen concentration and metal corrosion control, instrumentation, thermal-hydraulic performance of heat exchangers and recuperators, and free convection and forced pumping. This paper discusses the technology development and lessons learned from the operation of this facility. A LBE test loop has been operational since December 2001. Using procedures, training, and engineering controls, this loop has operated without an accident. Continuous improvements in operation procedures and instrumentation over these years have resulted in a facility of high reliability, providing the groundwork for the use of LBE as a reactor coolant for temperatures up to 550 C.

The feasibility of producing directionally solidified eutectic alloy composites by edge-defined, film-fed growth (EFG) was carried out. The three eutectic alloys which were investigated were gamma + delta, gamma/gamma prime + delta, and a Co-base TaC alloy containing Cr and Ni. Investigations into the compatibility and wettability of these metals with various carbides, borides, nitrides, and oxides disclosed that compounds with the largest (negative) heats of formation were most stable but poorest wetting. Nitrides and carbides had suitable stability and low contact angles but capillary rise was observed only with carbides. Oxides would not give capillary rise but would probably fulfill the other wetting requirements of EFG. Tantalum carbide was selected for most of the experimental portion of the program based on its exhibiting spontaneous capillary rise and satisfactory slow rate of degradation in the liquid metals. Samples of all three alloys were grown by EFG with the major experimental effort restricted to gamma + delta and gamma/gamma prime + delta alloys. In the standard, uncooled EFG apparatus, the thermal gradient was inferred from the growth speed and was 150 to 200 C/cm. This value may be compared to typical gradients of less than 100 C/cm normally achieved in a standard Bridgman-type apparatus. When a stream of helium was directed against the side of the bar during growth, the gradient was found to improve to about 250 C/cm. In comparison, a theoretical gradient of 700 C/cm should be possible under ideal conditions, without the use of chills. Methods for optimizing the gradient in EFG are discussed, and should allow attainment of close to the theoretical for a particular configuration.

The Gas Research Institute (GRI) estimates that by the year 2010, 40% or more of U.S. gas supply will be provided by supplements including substitute natural gas (SNG) from coal. These supplements must be cost competitive with other energy sources. The first generation technologies for coal gasification e.g. the Lurgi Pressure Gasification Process and the relatively newer technologies e.g. the KBW (Westinghouse) Ash Agglomerating Fluidized-Bed, U-Gas Ash Agglomerating Fluidized-Bed, British Gas Corporation/Lurgi Slagging Gasifier, Texaco Moving-Bed Gasifier, and Dow and Shell Gasification Processes, have several disadvantages. These disadvantages include high severities of gasification conditions, low methane production, high oxygen consumption, inability to handle caking coals, and unattractive economics. Another problem encountered in catalytic coal gasification is deactivation of hydroxide forms of alkali and alkaline earth metal catalysts by oxides of carbon (CO{sub x}). To seek solutions to these problems, a team consisting of Clark Atlanta University (CAU, a Historically Black College and University, HBCU), the University of Tennessee Space Institute (UTSI) and Georgia Institute of Technology (Georgia Tech) proposed to identify suitable low melting eutectic salt mixtures for improved coal gasification. The research objectives of this project were to: Identify appropriate eutectic salt mixture catalysts for coal gasification; Assess agglomeration tendency of catalyzed coal; Evaluate various catalyst impregnation techniques to improve initial catalyst dispersion; Determine catalyst dispersion at high carbon conversion levels; Evaluate effects of major process variables (such as temperature, system pressure, etc.) on coal gasification; Evaluate the recovery, regeneration and recycle of the spent catalysts; and Conduct an analysis and modeling of the gasification process to provide better understanding of the fundamental mechanisms and kinetics of the process.

The influence of the ternary alloying elements Cu, Mg and Fe on the Al-Si eutectic microstructure is investigated using a commercial purity Al-10 wt%Si alloy in unmodified and Sr-modified conditions. A change in the Al-Si eutectic microstructure was associated with a change in the nucleation density of the eutectic grains caused by the addition of ternary alloying elements. When the ternary alloying element addition resulted in an increase in the eutectic nucleation frequency, a fibrous to flake-like transition was observed within the eutectic grain. When the ternary alloying element addition decreased the eutectic nucleation frequency significantly, a change in the eutectic morphology from flake-like to a mixture of flake-like and fibrous morphologies was observed. The mechanism of Al-Si eutectic modification is discussed. The growth velocity of the eutectic grain - liquid interface and the constitutional driving force available for growth are proposed as important parameters that influence the degree of eutectic modification in Al-Si alloys.

The performance of Ti alloys can be considerably enhanced by combining Ti and other elements, causing an eutectic transformation and thereby producing composites in situ from the liquid phase. This paper reports on the processing and characterization of a directionally solidified Ti-Fe eutectic alloy. Directional solidification at different growth rates was carried out in a setup that employs a water-cooled copper crucible combined with a voltaic electric arc moving through the sample. The results obtained show that a regular fiber-like eutectic structure was produced and the interphase spacing was found to be a function of the growth rate. Mechanical properties were measured using compression, microindentation and nanoindentation tests to determine the Vickers hardness, compressive strength and elastic modulus. Directionally solidified eutectic samples presented high values of compressive strength in the range of 1844-3000 MPa and ductility between 21.6 and 25.2%.

The effect of boron on the microstructure of a near-eutectic Al-Si alloy (ZL109) was investigated by scanning electron microscopy (SEM) and electron beam microprobe analysis (EPMA). It was found that {alpha}-Al dendrites and eutectic clusters were significantly refined by the addition of boron. Another interesting discovery is that the near-eutectic alloy exhibited hypereutectic structure characteristics when the level of boron added exceeds 0.3%, i.e., primary Si is precipitated in the eutectic microstructure. A new type of nucleation substrate for the primary Si is found, Al {sub x}Ca {sub m}B {sub n}Si. This appears to be the main reason for the precipitation of primary Si.

Increased densification rates were found as much as 200/sup 0/C below the eutectic temperature (980/sup 0/C) for MgF/sub 2/ containing small amounts of CaF/sub 2/. Constant heating rate and constant temperature sintering data, as well as microstructural developments indicated that solid state grain-boundary transport rates had been enhanced by the eutectic forming additive. The effect saturated at about 1 wt % CaF/sub 2/. The results suggest that densification of ceramic powders could be favorably affected without a substantial increase in the grain growth rate, by the addition of small amounts of eutectic forming additives, and sintering below the eutectic temperature. 6 figures.

National Institute of Metrology (NIM) (China) and National Physical Laboratory (NPL) (UK) have collaborated to construct metal-carbon eutectic alloy fixed points at NPL. A modified NPL Thermogauge furnace was vertically used to construct fixed points of Pd-C, Pt-C, Ru-C, and Ir-C. Breakage of Pd-C and Ru-C cells was traced to changes in furnace temperature gradients resulting from changing from horizontal to vertical operation. Subsequently, it was found that positioning the cell being filled so that the metal melting always starts from the top and freezing from the bottom to solve this problem. The constructed Pt-C cell was then compared to a Pt-C fixed point previously constructed by NIM. The results indicate that the two cells made independently agreed to be better than 40 mK.

A dissimilar joint of AA5083 Al alloy and copper was produced by friction spot welding. The Al-MgCuAl{sub 2} eutectic in both coupled and divorced manners were found in the weld. At a relatively high temperature, mass transport of Cu due to plastic deformation, material flow, and atomic diffusion, combined with the alloy system of AA5083 are responsible for the ternary eutectic melting.

3D mesostructured AgCl-KCl photonic crystals emerge from colloidal templating of eutectic solidification. Solvent removal of the KCl phase results in a mesostructured AgCl inverse opal. The 3D-template-induced confinement leads to the emergence of a complex microstructure. The 3D mesostructured eutectic photonic crystals have a large stop band ranging from the near-infrared to the visible tuned by the processing. PMID:26177830

A dissimilar joint of AA5083 Al alloy and copper was produced by friction spot welding. The Al-MgCuAl2 eutectic in both coupled and divorced manners were found in the weld. At a relatively high temperature, mass transport of Cu due to plastic deformation, material flow, and atomic diffusion, combined with the alloy system of AA5083 are responsible for the ternary eutectic melting.

NiAl-based eutectic alloys, consisting of an ordered bcc matrix (B2) and disordered bcc fibers (A2), have been a subject of intensive efforts aimed at tailoring the properties of many of the currently used nickel-based superalloys. A thermodynamic phase field model was developed on a thermodynamic foundation and fully integrated with a thermo-kinetic database of the Ni-Al-Cr ternary system to elucidate the resulting peculiar eutectic microstructure. Invoking a variation of the liquid/solid interfacial thickness with temperature, we simulated the characteristic sunflower-like eutectic microstructures in the NiAl-Cr composites, consistent with experimental observations. The mechanism that governs the formation of the peculiar eutectic morphology was envisioned from the modeled evolutions associated with six sequential steps. Our calculations show that the conditional spinodal decomposition occurring in sequence could further trim and revise the microstructure of the eutectics by generating fine-domain structures, thereby providing an additional method to explore the novel NiAl-based eutectic composites with tunable properties at elevated temperatures. PMID:27385194

Crystallization of colloids has extensively been studied for past few decades as models to study phase transition in general. Recently, complex crystal structures in multi-component colloids, including alloy and eutectic structures, have attracted considerable attention. However, the fabrication of 2D area-filling colloidal eutectics has not been reported till date. Here, we report formation of eutectic structures in binary and ternary aqueous colloids due to depletion attraction. We used charged particles + linear polyelectrolyte systems, in which the interparticle interaction could be represented as a sum of the electrostatic, depletion, and van der Waals forces. The interaction was tunable at a lengthscale accessible to direct observation by optical microscopy. The eutectic structures were formed because of interplay of crystallization of constituent components and accompanying fractionation. An observed binary phase diagram, defined by a mixing ratio and inverse area fraction of the particles, was analogous to that for atomic and molecular eutectic systems. This new method also allows the adjustment of both the number and wavelengths of Bragg diffraction peaks. Furthermore, these eutectic structures could be immobilized in polymer gel to produce self-standing materials. The present findings will be useful in the design of the optical properties of colloidal crystals.

The temperature and enthalpy of transformations of organic alloys from the binary system succinonitrile-(D)camphor were measured by means of differential scanning calorimetry (DSC) within the entire composition range. The analytical description of the Gibbs energies of pure succinonitrile (SCN) and pure (D)camphor (DC) were derived utilizing the data on temperature and enthalpy of transformations, and temperature dependencies of heat capacity available in the literature. The phase diagram for the binary SCN-DC system was assessed via the CALPHAD approach using Thermo-Calc by simultaneously optimizing the thermodynamic and phase equilibrium data available in the literature and measured in the present work. A good agreement between the experimental and calculated data for the phase diagram as well as for the thermochemical properties was achieved. Experiments and calculations show that the binary system SCN-DC has an eutectic reaction with the eutectic point at 311.5 K and 13.9 mol% DC. The enthalpy of mixing derived in the optimisation proves weak attractive interaction between dissimilar molecules. Unidirectional solidification of the eutectic alloy was performed in order to verify the nature of the eutectic: we find that eutectic growth occurs with both solid phases being nonfacetted and with a rod-like eutectic structure consisting of 23 vol% (DC) and 77 vol% (SCN). Due to the optical activity of DC its distribution in the solid sample is well detectible in polarised light.

Controlling the growth of eutectic Si and thereby modifying the eutectic Si from flake-like to fibrous is a key factor in improving the properties of Al-Si alloys. To date, it is generally accepted that the impurity-induced twinning (IIT) mechanism and the twin plane re-entrant edge (TPRE) mechanism as well as poisoning of the TPRE mechanism are valid under certain conditions. However, IIT, TPRE or poisoning of the TPRE mechanism cannot be used to interpret all observations. Here, we report an atomic-scale experimental and theoretical investigation on the roles of Eu during the growth of eutectic Si in Al-Si alloys. Both experimental and theoretical investigations reveal three different roles: (i) the adsorption at the intersection of Si facets, inducing IIT mechanism, (ii) the adsorption at the twin plane re-entrant edge, inducing TPRE mechanism or poisoning of the TPRE mechanism, and (iii) the segregation ahead of the growing Si twins, inducing a solute entrainment within eutectic Si. This investigation not only demonstrates a direct experimental support to the well-accepted poisoning of the TPRE and IIT mechanisms, but also provides a full picture about the roles of Eu atoms during the growth of eutectic Si, including the solute entrainment within eutectic Si. PMID:26328541

Controlling the growth of eutectic Si and thereby modifying the eutectic Si from flake-like to fibrous is a key factor in improving the properties of Al-Si alloys. To date, it is generally accepted that the impurity-induced twinning (IIT) mechanism and the twin plane re-entrant edge (TPRE) mechanism as well as poisoning of the TPRE mechanism are valid under certain conditions. However, IIT, TPRE or poisoning of the TPRE mechanism cannot be used to interpret all observations. Here, we report an atomic-scale experimental and theoretical investigation on the roles of Eu during the growth of eutectic Si in Al-Si alloys. Both experimental and theoretical investigations reveal three different roles: (i) the adsorption at the intersection of Si facets, inducing IIT mechanism, (ii) the adsorption at the twin plane re-entrant edge, inducing TPRE mechanism or poisoning of the TPRE mechanism, and (iii) the segregation ahead of the growing Si twins, inducing a solute entrainment within eutectic Si. This investigation not only demonstrates a direct experimental support to the well-accepted poisoning of the TPRE and IIT mechanisms, but also provides a full picture about the roles of Eu atoms during the growth of eutectic Si, including the solute entrainment within eutectic Si. PMID:26328541

Vertical light-emitting diodes (VLEDs) have attracted considerable attention owing to their improved thermal, electrical, and optical performance compared to conventional LEDs. To fabricate VLEDs, a bonding technique is required following laser lift-off. Eutectic bonding techniques are preferred owing to their low-heat mechanism and production safety. However, the conventional resistance heating method for eutectic bonding process, the extremely longer process time becomes a problem such as cost rise, wapage. In this study, the thermal efficiency was measured according to the diameter of the coil in order to optimize the eutectic bonding of the RF induction heating method in order to solve this problem. We confirmed that successful eutectic bonding is possible with less than 30 min processing using Sn-Glass. In addition, Au (20 wt%)/Sn (80 wt%) alloy, a mainly used the eutectic bonding interlayer material for VLEDs, can also be used as an interlayer to provide void-free eutectic bonding in less than 30 min. PMID:26726547

Controlling the growth of eutectic Si and thereby modifying the eutectic Si from flake-like to fibrous is a key factor in improving the properties of Al-Si alloys. To date, it is generally accepted that the impurity-induced twinning (IIT) mechanism and the twin plane re-entrant edge (TPRE) mechanism as well as poisoning of the TPRE mechanism are valid under certain conditions. However, IIT, TPRE or poisoning of the TPRE mechanism cannot be used to interpret all observations. Here, we report an atomic-scale experimental and theoretical investigation on the roles of Eu during the growth of eutectic Si in Al-Si alloys. Both experimental and theoretical investigations reveal three different roles: (i) the adsorption at the intersection of Si facets, inducing IIT mechanism, (ii) the adsorption at the twin plane re-entrant edge, inducing TPRE mechanism or poisoning of the TPRE mechanism, and (iii) the segregation ahead of the growing Si twins, inducing a solute entrainment within eutectic Si. This investigation not only demonstrates a direct experimental support to the well-accepted poisoning of the TPRE and IIT mechanisms, but also provides a full picture about the roles of Eu atoms during the growth of eutectic Si, including the solute entrainment within eutectic Si.

Crystallization of colloids has extensively been studied for past few decades as models to study phase transition in general. Recently, complex crystal structures in multi-component colloids, including alloy and eutectic structures, have attracted considerable attention. However, the fabrication of 2D area-filling colloidal eutectics has not been reported till date. Here, we report formation of eutectic structures in binary and ternary aqueous colloids due to depletion attraction. We used charged particles + linear polyelectrolyte systems, in which the interparticle interaction could be represented as a sum of the electrostatic, depletion, and van der Waals forces. The interaction was tunable at a lengthscale accessible to direct observation by optical microscopy. The eutectic structures were formed because of interplay of crystallization of constituent components and accompanying fractionation. An observed binary phase diagram, defined by a mixing ratio and inverse area fraction of the particles, was analogous to that for atomic and molecular eutectic systems. This new method also allows the adjustment of both the number and wavelengths of Bragg diffraction peaks. Furthermore, these eutectic structures could be immobilized in polymer gel to produce self-standing materials. The present findings will be useful in the design of the optical properties of colloidal crystals. PMID:26984298

The liquid to solid transformation of ternary Ag42.4Cu21.6Sb36 eutectic alloy was accomplished in an ultrasonic field with a frequency of 35 kHz, and the growth mechanism of this ternary eutectic was examined. Theoretical calculations predict that the sound intensity in the liquid phase at the solidification interface increases gradually as the interface moves up from the sample bottom to its top. The growth mode of ( ɛ + θ + Sb) ternary eutectic exhibits a transition of “divorced eutectic—mixture of anomalous and regular structures—regular eutectic” along the sample axis due to the inhomogeneity of sound field distribution. In the top zone with the highest sound intensity, the cavitation effect promotes the three eutectic phases to nucleate independently, while the acoustic streaming efficiently suppresses the coupled growth of eutectic phases. In the meantime, the ultrasonic field accelerates the solute transportation at the solid-liquid interface, which reduces the solute solubility of eutectic phases.

The solidification characteristics of three types of Pb-Sb-Sn ternary alloys with different primary phases were studied under substantial undercooling conditions. The experimental results show that primary (Pb) and SbSn phases grow in the dendritic mode, whereas primary (Sb) phase exhibits faceted growth in the form of polygonal blocks and long strips. (Pb) solid solution phase displays strong affinity with SbSn intermetallic compound so that they produce various morphologies of pseudobinary eutectics, but it can only grow in the divorced eutectic mode together with (Sb) phase. Although (Sb) solid solution phase and SbSn intermetallic compound may grow cooperatively within ternary eutectic microstructures, they seldom form pseudobinary eutectics independently. The (Pb)+(Sb)+SbSn ternary eutectic structure usually shows lamellar morphology, but appears as anomalous eutectic when its volume fraction becomes small. EDS analyses reveal that all of the three primary (Pb), (Sb) and SbSn phases exhibit conspicuous solute trapping effect during rapid solidification, which results in the remarkable extension of solute solubility.

Crystallization of colloids has extensively been studied for past few decades as models to study phase transition in general. Recently, complex crystal structures in multi-component colloids, including alloy and eutectic structures, have attracted considerable attention. However, the fabrication of 2D area-filling colloidal eutectics has not been reported till date. Here, we report formation of eutectic structures in binary and ternary aqueous colloids due to depletion attraction. We used charged particles + linear polyelectrolyte systems, in which the interparticle interaction could be represented as a sum of the electrostatic, depletion, and van der Waals forces. The interaction was tunable at a lengthscale accessible to direct observation by optical microscopy. The eutectic structures were formed because of interplay of crystallization of constituent components and accompanying fractionation. An observed binary phase diagram, defined by a mixing ratio and inverse area fraction of the particles, was analogous to that for atomic and molecular eutectic systems. This new method also allows the adjustment of both the number and wavelengths of Bragg diffraction peaks. Furthermore, these eutectic structures could be immobilized in polymer gel to produce self-standing materials. The present findings will be useful in the design of the optical properties of colloidal crystals. PMID:26984298

A pseudo-binary eutectic, in which the intermetallic Ni7Hf2 reinforces the Ni-Cr solid solution phase, was previously predicted in the Ni-Cr-Hf system by a computer analysis. The experimental determination of pseudo binary eutectic compositions and the directional solidification of the Ni-Cr-Hf, Zr, and Ni-Cr-Zr eutectic alloys are discussed. To determine unknown eutectics, chemical analyses were made of material bled from near eutectic ingots during incipient melting. Nominal compositions in weight percent of Ni-18.6Cr-24.0HF, Ni19.6Cr-12.8Zr-2.8Hf, and Ni-19.2Cr-14.8Zr formed aligned pseudo-binary eutectic structures. The melting points were about 1270 C. The reinforcing intermetallic phases were identified as noncubic (Ni,Cr)7Hf2 and (Ni,Cr)7(Hf,Zr)2, and face centered cubic (Ni,Cr)5Zr. The volume fraction of the reinforcing phases were about 0.5.

Chisel-quarried recycled granite in MA is datable by runes to 1069 CE; it could corroborate dating by a LIDAR. Associated sites, possibly used by Vikings to dry-dock their ships, could have exploited lock-like controls, possibly a continued technology. Site-leveling at the Giza Pyramids proves water was used. `Locks' and body-immersion worked for building, moving, erecting, or watering, at sites like Stonehenge, The Hanging Gardens at Babylon, the Moas of Easter Island, or The Pyramids, where the eroding water discharge was deliberately flushed over the Sphinx complex. It enhance the electromagnetically excited blue light signals we can detect, especially at sites frequented by Molocket of ME. Information, as at America's Stonehenge, in NH, and constructions at Acton MA, at Giza or at Rumford ME proves that the Pyramids and Sphinx were engineered and built about 4500 BP.

Galactic bulge microlensing surveys provide a probe of Galactic structure. We present the first field-by-field comparison between microlensing observations and the Besançon population synthesis Galactic model. Using an updated version of the model we provide maps of optical depth, average event duration and event rate for resolved source populations and for difference imaging analysis (DIA) events. We also compare the predicted event time-scale distribution to that observed. The simulation follows the selection criteria of the MOA-II survey. We modify the Besançon model to include M dwarfs and brown dwarfs. Our best-fitting model requires a brown dwarf mass function slope of -0.4. The model provides good agreement with the observed average duration, and respectable consistency with the shape of the time-scale distribution (reduced χ2 ≃ 2.2). The DIA and resolved source limiting yields bracket the observed number of events by MOA-II (2.17 × and 0.83 × the number observed, respectively). We perform a two-dimensional fit to the event spatial distribution to predict the optical depth and event rate across the Galactic bulge. The most serious difficulty for the model is that it provides only ˜50 per cent of the measured optical depth and event rate per star at low Galactic latitude around the inner bulge (|b| < 3°). This discrepancy most likely is associated with known underestimated extinction and star counts in the innermost regions and therefore provides additional support for a missing inner stellar population.

Genetic toxicity testing has traditionally been used for hazard identification, with dichotomous classification of test results serving to identify genotoxic agents. However, the utility of genotoxicity data can be augmented by employing dose-response analysis and point of departure determination. Via interpolation from a fitted dose-response model, the benchmark dose (BMD) approach estimates the dose that elicits a specified (small) effect size. BMD metrics and their confidence intervals can be used for compound potency ranking within an endpoint, as well as potency comparisons across other factors such as cell line or exposure duration. A recently developed computational method, the BMD covariate approach, permits combined analysis of multiple dose-response data sets that are differentiated by covariates such as compound, cell type or exposure regime. The approach provides increased BMD precision for effective potency rankings across compounds and other covariates that pertain to a hypothesised mode of action (MOA). To illustrate these applications, the covariate approach was applied to the analysis of published in vitro micronucleus frequency dose-response data for ionising radiations, a set of aneugens, two mutagenic azo compounds and a topoisomerase II inhibitor. The ionising radiation results show that the precision of BMD estimates can be improved by employing the covariate method. The aneugen analysis provided potency groupings based on the BMD confidence intervals, and analyses of azo compound data from cells lines with differing metabolic capacity confirmed the influence of endogenous metabolism on genotoxic potency. This work, which is the first of a two-part series, shows that BMD-derived potency rankings can be employed to support MOA evaluations as well as facilitate read across to expedite chemical evaluations and regulatory decision-making. The follow-up (Part II) employs the combined covariate approach to analyse in vivo genetic toxicity dose

The current work explores the effects of a small addition of Ni on the microstructure and mechanical properties of Sn-Zn eutectic solder alloy (Sn-14.9 at.%Zn). In two sets of experiments, Ni is either added to the eutectic alloy or Zn in the eutectic alloy is replaced by an increasing amount of Ni. The study indicates that small additions of Ni in eutectic Sn-Zn solder (˜0.017 at.%) refines the eutectic microstructure together with the appearance of the small amount of primary Zn plates. Increasing the Ni content to 0.142 at.% and beyond, then an intermetallic phase ϒ-Ni5Zn21 with dendritic morphology appears in the microstructure along with dendrites of primary Sn. The scale of eutectic microstructure shows a decreasing trend till 0.902 at.%Ni with eutectic spacing of 1.98 ± 0.32 μm for this alloy. Further addition of Ni coarsens the microstructure. The replacement of Zn with Ni in the eutectic composition follows a similar trend with a lesser refinement of the microstructure. In both the scenarios, the addition of a small amount of Ni increases the eutectic temperatures till a critical concentration is reached beyond which one can observe a decrease in the eutectic point. The trend is similar for the solid solubility of Zn in Sn while the trend is opposite for the measured eutectic composition, which decreases at the initial stages of Ni addition. Through a detailed measurement of mechanical properties, the study establishes significant improvement of the strength of Sn-Zn solder with small additions of Ni in the alloy with a maximum hardness of 26 ± 1 HV and 0.2% proof stress of 72 ± 3 MPa at room temperature for the eutectic alloy with 0.902 at.%Ni.

One lamellar eutectic sample and one fiber-like eutectic sample were solidified directionally during the TEXUS-6 rocket flight. The microstructures and the results of the thermal analysis, obtained from the temperatures recorded on the cartridge skin, are compared. No appreciable modifications of the regularity of the eutectic structures were observed by passing from 1 g to 0.0001 g in these experiments. No steady state growth conditions were achieved in these experiments.

The study addresses the effect of systematically varying gamma-gamma-prime eutectic content and porosity level on the fatigue life of a hydrogen-charged single crystal PWA 1480 superalloy. Four microstructural variants are produced, and differences in gamma-gamma-prime eutectic morphology among the four processing variants are analyzed. Single valued tensile test data indicate that the tensile and yield strength of the PWA 1480 are degraded by hydrogen charging, with the exception of the material given a eutectic solution treatment. It is shown that the reduction of the fatigue life can be minimized by a duplex thermomechanical treatment consisting of a eutectic solution followed by hot isostatic pressing.

Deep eutectic solvents (DESs) have emerged as a new type of promising ionic solvents with a broad range of potential applications. Although their ecotoxicological profile is still poorly known, DESs are generally regarded as "green" because they are composed of ammonium salts and H-bond donors (HBDs) which are considered to be eco-friendly. In this work, cholinium-based DESs comprised of choline chloride (ChCl) and choline acetate (ChAc) as the salt and urea (U), acetamide (A), glycerol (G) and ethylene glycol (EG) as the HBD were evaluated for their toxic effects on different living organisms such as Escherichia coli (a bacterium), Allium sativum (garlic, a plant) and hydra (an invertebrate), and their biodegradabilities were assessed by means of closed bottle tests. These DESs possessed an anti-bacterial property and exhibited inhibitory effects on the test organisms adopted, depending on the composition and concentration of the DES. The mechanism for the impact of DESs and their components on different living organisms can be associated to their interactions with the cellular membranes. Not all DESs can be considered readily biodegradable. By extending the limited knowledge about the toxicity and biodegradation of this particular solvent family, this investigation on DESs provides insight into our structure-based understanding of their ecotoxicological behavior. PMID:25800513

Deep eutectic solvents (DES) are mixtures of two or more components with high melting temperatures, which form a liquid at room temperature. These DES hold great promise as green solvents for chemical processes, as they are inexpensive and environmentally friendly. Specifically, they present a unique solvating environment to polymers that is different from water. Here, we use small angle neutron scattering to study the polymer properties of the common, water-soluble, polyvinylpyrrolidone (PVP) in the prominent DES formed by a 1:2 molar mixture of choline chloride and urea. We find that the polymer adopts a slightly different structure in DES than in water, so that at higher concentrations the polymer favors a more expanded conformation compared to the same concentration in water. Yet, the osmotic pressure of PVP solutions in DES is very similar to that in water, indicating that both solvents are of comparable quality and that the DES components interact favorably with PVP. The osmotic pressure measurements within this novel class of promising solvents should be of value toward future technological applications as well as for osmotic stress experiments in nonaqueous environments. PMID:26963367

One of the most important sets of model prebiotic experiments consists of reactions that synthesize complementary oligonucleotides from preformed templates under nonenzymatic conditions. Most of these experiments are conducted at 4 degrees C using 0.01-0.1 M concentrations of activated nucleotide monomer and template (monomer equivalent). In an attempt to extend the conditions under which this type of reaction can occur, we have concentrated the reactants by freezing at -18 degrees C, which is close to the NaCl-H2O eutectic at -21 degrees C. The results from this set of experiments suggest that successful syntheses can occur with poly(C) concentrations as low at 5 x 10(-4) M and 2MeImpG concentrations at 10(-3) M. It was also anticipated that this mechanism might allow the previously unsuccessful poly(A)-directed synthesis of oligo(U)s to occur. However, no template effect was seen with the poly(A) and ImpU system. The failure of these conditions to allow template-directed synthesis of oligo(U)s supports the previously proposed idea that pyrimidines may not have been part of the earliest genetic material. Because of the low concentrations of monomer and template that would be expected from prebiotic syntheses, this lower temperature could be considered a more plausible geologic setting for template-directed synthesis than the standard reaction conditions.

Very recently our group has produced novel agar-based fibers by an electrospinning technique using water as solvent and polyvinyl alcohol (PVA) as co-blending polymer. Here, we tested the deep eutectic solvent (DES), (2-hydroxyethyl)trimethylammonium chloride/urea prepared at 1:2 molar ratio, as an alternative solvent medium for agar electrospinning. The electrospun materials were collected with an ethanol bath adapted to a previous electrospinning set-up. One weight percent agar-in-DES showed improved viscoelasticity and hence, spinnability, when compared to 1 wt% agar-in-water and pure agar nanofibers were successfully electrospun if working above the temperature of sol-gel transition (∼80 °C). By changing the solvent medium we decreased the PVA concentration (5 wt% starting solution) and successfully produced composite fibers with high agar contents (50/50 agar/PVA). Best composite fibers were formed with the 50/50 and 30/70 agar/PVA solutions. These fibers were mechanically resistant, showed tailorable surface roughness and diverse size distributions, with most of the diameters falling in the sub-micron range. Both nano and micro forms of agar fibers (used separately or combined) may have potential for the design of new and highly functional agar-based materials. PMID:26116384

An aluminum-germanium eutectic bonding technology has been used to uniformly bond two silicon wafers for MEMS packaging at temperatures as low as 450 °C, well below the aluminum-silicon eutectic temperature (577 °C). A device silicon wafer has been put in contact with a cap wafer where an aluminum film covered by a germanium film has been thermally evaporated. The annealing has been performed in a vacuum furnace under uniaxial pressure variable from 1.8 up to 30 kbar. The samples have been analyzed with various analytical techniques. 4He+ MeV Rutherford Backscattering Spectrometry (RBS) has been used to measure the thicknesses of the deposited films and to follow the aluminum-germanium intermixing, Scanning Acoustic Microscope (SAM) to control the uniformity of the bonding, Scanning Electron Microscope (SEM) associated with electron induced X-ray fluorescence to analyze composition, morphology and elements distribution in the film between the two bonded wafers. The temperatures for the annealing were selected above and below the Ge-Al the eutectic temperature. At temperatures below the eutectic no-bonding has been obtained for any applied pressure. Above the eutectic bonding occurs. The formation of a liquid film is mandatory to obtain a reproducible and robust bonding. The pressure is necessary to improve the contacts between the two wafers; its role in the metallurgy of the bonding needs to be explored.

The factors that influence the shape of the solid-liquid interface of a lamellar binary eutectic alloy are evaluated. Alloys of carbon tetrabromide and hexachloroethane which serve as a transparent analogue of lamellar metallic eutectics are used. The observed interface shapes are analyzed by computer-aided methods. The solid-liquid interfacial free energies of each of the individual phases comprising the eutectic system are measured as a function of composition using a 'grain boundary groove' technique. The solid-liquid interfacial free energy of the two phases are evaluated directly from the eutectic interface. The phase diagram for the system, the heat of fusion as a function of composition, and the density as a function of composition are measured. The shape of the eutectic interface is controlled mainly by the solid-liquid and solid-solid interfacial free energy relationships at the interface and by the temperature gradient present, rather than by interlamellar diffusion in the liquid at the interface, over the range of growth rates studied.

Deep eutectic solvents promoted the stabilization of the collapsed state of elastin-like recombinamers - and the subsequent formation of aggregates - upon the loss of the structural water molecules involved in hydrophobic hydration. Cryo-etch scanning electron microscopy allowed the observation of these aggregates in neat deep eutectic solvents. The suppression of the lower critical solution temperature transition, observed by differential scanning calorimetry and dynamic light scattering, confirmed the presence of the elastin-like recombinamers in their collapsed state. Actually, the transition from the collapsed to the expanded state was suppressed even after moderate aqueous dilution - for water contents ranging from nil to ca. 45 wt % - and it was only recovered upon further addition of water - above 50 wt %. These features revealed the preferred stabilization of the collapsed state in not only neat deep eutectic solvents but also partially hydrated deep eutectic solvents. We consider that the capability to trigger the lower critical solution temperature transition by partial hydration of deep eutectic solvent may open interesting perspectives for nano(bio)technological applications of elastin-like recombinamers. PMID:22632070

High-temperature eutectic fixed points have proved to be convenient tools for temperature scale dissemination and thermometer calibrations/checks at temperatures above 1100°C. In order to investigate the feasibility of metal-carbon eutectic cells in industrial applications as a means for assessing the traceability of non-contact thermometers, a batch of cells was constructed at LNE-Cnam, NPL, and TUBITAK UME. Compared to the usual dimensions of high-temperature fixed point cells (45 mm in length × 24 mm in diameter), a new cell design was created to fit with industrial applications. TUBITAK UME constructed and characterized five ruthenium-carbon (Ru-C) eutectic cells of dimensions 24 mm in length × 24 mm in diameter. One of these cells has been selected and characterized at CEA premises. Ru-C eutectic cells have been evaluated in terms of short-term repeatability, reproducibility, furnace effect, sharp temperature ramps, and the effect of cell location. Measurements at TÜBİTAK UME have been performed with a transfer standard pyrometer calibrated at the copper point and a BB3500pg high-temperature blackbody furnace was used for construction and measurement. For the measurements at CEA, a Land Standard—HIMERT S1 radiation thermometer and a VITI induction furnace were used. In this article results of the measurements at TÜBİTAK UME and CEA will be presented. The possible use of these mini-eutectic cells as industrial temperature standards will be discussed.

A directionally solidified alloy based on the NiAl-(Cr, Mo) eutectic was examined by transmission and scanning electron microscopy to characterize the microstructure and room temperature deformation and fracture behavior. The microstructure consisted of a lamellar morphology with a group of zone axes (111) growth direction for both the NiAl and (Cr, Mo) phases. The interphase boundary between the eutectic phases was semicoherent and composed of a well-defined dislocation network. In addition, a fine array of coherent NiAl precipitates was dispersed throughout the (Cr, Mo) phase. The eutectic morphology was stable at 1300 K with only coarsening of the NiAl precipitates occurring after heat treatment for 1.8 ks (500 h). Fracture of the aligned eutectic is characterized primarily by a crack bridging/renucleation mechanism and is controlled by the strength of the semicoherent interface between the two phases. However, contributions to the toughness of the eutectic may arise from plastic deformation of the NiAl phase and the geometry associated with the fracture surface.

The polonium contamination hazard arise as a result of accidental Po-210 release from breeding blanket material - melted Li17Pb83 eutectic - in the environment. The experimental study of Po-210 release rates from eutectic were carry out in atmosphere of noble gases and air with different humidity in 1992-1993. In these experiments used method of carrier-gas flowing above melted eutectic surface. The main findings presented by RDIPE and Karpov Institute are: (1) The polonium-210 release rate strongly increase with eutectic temperature from 150 to 450{degrees}C. (2) The Po-210 release rate in the noble carrier-gas is in proportion with polonium concentration in eutectic in studied range from 10{sup {minus}7} to 10{sup {minus}4} Ci/g. (3) The Po-210 release rate in air remarkably effected by the surface oxide film also. (4) In these experiments for the first time were studied differently gaseous and aerosol polonium-210 fractions release rates. The experimental results and corresponding estimates showed needs the technological and accidental cleaning systems equipped by complex filters of gaseous and aerosols polonium-210 forms.

The manufacturing of components for operation at high temperatures requires the use of metallic materials which can keep satisfactory mechanical and chemical properties, even at temperatures beyond 1000°C. An interesting alternative to solve such a problem is the use of directionally solidified eutectic alloys. A potentially promising system for the manufacture of structural materials, and so far not totally studied, is the eutectic based on the Fe-Al-Nb system, which involves the (FeAl) 2Nb phase and the FeAl solid solution. Eutectic samples from this system were directionally solidified in a vertical Bridgman crystal growth unit. The objective of the experiments was to determine the influence of the growth rate on the eutectic microstructure. The ingots obtained were investigated by using optical and electron scanning microscopy. At low growth rate, the eutectic microstructure remained regular, even though it showed several types of microstructure defects. As the growth rate was increased, a transition from lamellar to fibrous morphology was observed.

In a radioactive material (RAM) packaging, the formation of eutectic at the Pu/SS (plutonium/stainless steel) interface is a serious concern and must be avoided to prevent of leakage of fissile material to the environment. The eutectic temperature for the Pu/SS is rather low (410 C) and could seriously impact the structural integrity of the containment vessel under accident conditions involving fire. The 9975 packaging is used for long term storage of Pu bearing materials in the DOE complex where the Pu comes in contact with the stainless steel containment vessel. Due to the serious consequences of the containment breach at the eutectic site, the Pu/SS interface temperature is kept well below the eutectic formation temperature of 410 C. This paper discusses the thermal models and the results for the extended fire conditions (1500 F for 86 minutes) that exist in a long term storage facility and concludes that the 9975 packaging Pu/SS interface temperature is well below the eutectic temperature.

A novel route for controlled synthesis of Prussian blue nanospheres (PB NSs) with different sizes by using deep eutectic solvents (DES) as both solvent and template provider was demonstrated. The size-controlled PB NSs were obtained directly by the coordination of Fe(CN)64- ion with Fe3+ ion in the DES. The probable mechanism of formation of PB NSs was discussed based on the characterization results of UV-visible, X-ray diffraction, X-ray photoelectronic spectrum and transfer electron microscopy. Furthermore, the electrochemical and electrocatalytic properties of the synthesized PB NSs were investigated, and it has demonstrated that the PB NSs exhibited excellent catalytic activity for H2O2 reduction, and then extended this strategy to glucose sensing, by detecting H2O2 formed from the enzymatic reaction of glucose oxidase with its substrate glucose. The linear calibration range for glucose was from 0.9 μM to 0.12 mM, with a correlation coefficient of 0.998. The limit of detection was 0.3 μM and the sensitivity was 61.7 A cm-2 M-1. The present study provides a general platform for the controlled synthesis of novel nanomaterials in DES and can be extended to other optical, electronic and magnetic nanocompounds.A novel route for controlled synthesis of Prussian blue nanospheres (PB NSs) with different sizes by using deep eutectic solvents (DES) as both solvent and template provider was demonstrated. The size-controlled PB NSs were obtained directly by the coordination of Fe(CN)64- ion with Fe3+ ion in the DES. The probable mechanism of formation of PB NSs was discussed based on the characterization results of UV-visible, X-ray diffraction, X-ray photoelectronic spectrum and transfer electron microscopy. Furthermore, the electrochemical and electrocatalytic properties of the synthesized PB NSs were investigated, and it has demonstrated that the PB NSs exhibited excellent catalytic activity for H2O2 reduction, and then extended this strategy to glucose sensing, by

Four kinds of green deep eutectic solvent (DES) were synthesized, including choline chloride (ChCl)-urea, tetramethylammonium chloride (TMACl)-urea, tetrapropylammonium bromide (TPMBr)-urea and ChCl-methylurea. An aqueous two-phase system (ATPS) based ChCl-urea DES was studied for the first time for the extraction of bovine serum albumin (BSA). Single factor experiments proved that the extraction efficiency of BSA was influenced by the mass of the DES, concentration of K2HPO4 solution, separation time and extraction temperature. The optimum conditions were determined through an orthogonal experiment with the four factors described above. The results showed that under the optimum conditions, the average extraction efficiency could reach up to 99.94%, 99.72%, 100.05% and 100.05% (each measured three times). The relative standard deviations (RSD) of extraction efficiencies in precision, repeatability and stability experiments were 0.5533% (n = 5), 0.8306% (n = 5) and 0.9829% (n = 5), respectively. UV-vis and FT-IR spectra confirmed that there were no chemical interactions between BSA and the DES in the extraction process, and the CD spectra proved that the conformation of BSA did not change after extraction. The conductivity, DLS and TEM were combined to investigate the microstructure of the top phase and the possible mechanism for the extraction. The results showed that hydrophobic interactions, hydrogen bonding interactions and the salting-out effect played important roles in the transfer process, and the aggregation and surrounding phenomenon were the main driving forces for the separation. All of these results proved that ionic liquid (IL)-based ATPSs could potentially be substituted with DES-based ATPSs to offer new possibilities in the extraction of proteins. PMID:24699681

In directional solidification of binary eutectics, it is often observed that two-phase lamellar growth patterns grow tilted with respect to the direction z of the imposed temperature gradient. This crystallographic effect depends on the orientation of the two crystal phases α and β with respect to z. Recently, an approximate theory was formulated that predicts the lamellar tilt angle as a function of the anisotropy of the free energy of the solid(α)-solid(β) interphase boundary. We use two different numerical methods-phase field (PF) and dynamic boundary integral (BI)-to simulate the growth of steady periodic patterns in two dimensions as a function of the angle θ(R) between z and a reference crystallographic axis for a fixed relative orientation of α and β crystals, that is, for a given anisotropy function (Wulff plot) of the interphase boundary. For Wulff plots without unstable interphase-boundary orientations, the two simulation methods are in excellent agreement with each other and confirm the general validity of the previously proposed theory. In addition, a crystallographic "locking" of the lamellae onto a facet plane is well reproduced in the simulations. When unstable orientations are present in the Wulff plot, it is expected that two distinct values of the tilt angle can appear for the same crystal orientation over a finite θ(R) range. This bistable behavior, which has been observed experimentally, is well reproduced by BI simulations but not by the PF model. Possible reasons for this discrepancy are discussed. PMID:25768518

All-atom molecular dynamics simulations have been carried out to investigate orientation jumps of acetamide molecules in three different ionic deep eutectics made of acetamide (CH3CONH2) and lithium salts of bromide (Br(–)), nitrate (NO3(–)) and perchlorate (ClO4(–)) at approximately 80:20 mole ratio and 303 K. Orientational jumps have been dissected into acetamide–acetamide and acetamide–ion catagories. Simulated jump characteristics register a considerable dependence on the anion identity. For example, large angle jumps are relatively less frequent in the presence of NO3(–) than in the presence of the other two anions. Distribution of jump angles for rotation of acetamide molecules hydrogen bonded (H-bonded) to anions has been found to be bimodal in the presence of Br(–) and is qualitatively different from the other two cases. Estimated energy barrier for orientation jumps of these acetamide molecules (H-bonded to anions) differ by a factor of ∼2 between NO3(–) and ClO4(–), the barrier height for the latter being lower and ∼0.5kBT. Relative radial and angular displacements during jumps describe the sequence ClO(4)– > NO3(–) > Br(–) and follow a reverse viscosity trend. Jump barrier for acetamide–acetamide pairs reflects weak dependence on anion identity and remains closer to the magnitude (∼0.7kBT) found for orientation jumps in molten acetamide. Jump time distributions exhibit a power law dependence of the type, P(tjump) ∝ A(tjump/τ)(−β), with both β and τ showing substantial anion dependence. The latter suggests the presence of dynamic heterogeneity in these systems and supports earlier conclusions from time-resolved fluorescence measurements. PMID:26131593

Most of the tasks on the project have successfully been completed and reported. A 12 month no-cost extension has been requested to complete the remaining tasks. This report summarizes the accomplishments of the first six months of the no-cost extensions period. The acetic acid extraction showed that acetic acid has more effect on the extraction of the ternary catalyst (LNK) ions than water. Based on the extraction results, the order of the recovery capability of Na{sub 2}CO{sub 3} using acetic acid, sulfuric acid and water extractions is sulfuric acid {ge} acetic acid > water; the order for K{sub 2}CO{sub 3} is sulfuric acid > water >acetic acid; and the order for Li{sub 2}CO{sub 3} is acetic acid > sulfuric acid >water. A process flowsheet for the catalyst recovery process was proposed based on the results. Scanning electron microscopy (SEM) studies showed most of the particles (coal) appear amorphous. Some coal particles are as large as 50-60 {micro}m, but most are smaller. One can also easily see a few crystalline particles (10-20 {micro}m) with sharp facets and corners. The electron micrographs of gasified char samples (reactor-aged) of the LNKcoal mixture showed that a dramatic change is obvious in the morphology and crystallinity of the sample and is consistent with the results obtained from the x-ray diffraction studies. XRD studies of reactor-aged samples showed a substantial increase in the sample crystallinity (due to the gasification of amorphous carbon). The eutectic salt presumably mostly converted to sulfates.

Studies have been performed on the effect of external compressive stress applied to samples of superplastic eutectic Bi-43 wt % Sn alloy during heating to a near-eutectic temperature on the specific heat of melting of the alloy. The alloy was prepared from chemically pure components by casting onto a massive copper substrate. After compression by ˜65% using a hydraulic press, the ingots were aged in air for approximately 7 months. The experiments were carried out using the method of differential thermal analysis. The samples were loaded using a specially designed device. A regular decrease in the specific heat of melting by ˜37% has been revealed while increasing the external pressure from 0 to 4.4 MPa. The experimental results are discussed using the available literature data on the heat of melting of the alloy and on the structure of the eutectic.

Freezing and melting of aqueous solutions of alkali halides confined in the cylindrical nanopores of MCM-41 and SBA-15 silica was probed by differential scanning calorimetry (DSC). We find that the confinement-induced shift of the eutectic temperature in the pores can be significantly greater than the shift of the melting temperature of pure water. Greatest shifts of the eutectic temperature are found for salts that crystallize as oligohydrates at the eutectic point. This behavior is explained by the larger fraction of pore volume occupied by salt hydrates as compared to anhydrous salts, on the assumption that precipitated salt constitutes an additional confinement for ice/water in the pores. A model based on this secondary confinement effect gives a good representation of the experimental data. Salt-specific secondary confinement may play a role in a variety of fields, from salt-impregnated advanced adsorbents and catalysts to the thermal weathering of building materials. PMID:27124392

Moa Valles is a well-preserved paleodrainage system that is nearly 300-km-long and carved into ancient highland terrains west of Idaeus Fossae. The paleofluvial system apparently originated from fluidized ejecta blankets, and it consists of a series of dam-breach paleolakes with associated fan-shaped sedimentary deposits. This paleofluvial system shows a rich morphological record of hydrologic activity in the highlands of Mars. Based on crater counting the latter activity seems to be Amazonian in age (2.43 - 1.41 Ga). This work is based on a digital elevation model (DEM) derived from Context camera (CTX) and High Resolution Imaging Science Experiment (HiRISE) stereo images. Our goals are to (a) study the complex channel flow paths draining into Idaeus Fossae after forming a series of dam-breach paleolakes and to (b) investigate the origin and evolution of this valley system with its implications for climate and tectonic control. The first part of the system is characterized by many paleolakes, which are interconnected and drain eastward into Liberta crater, forming a complex and multilobate deltaic deposit exhibiting a well-developed channelized distributary pattern with evidence of switching on the delta plain. A breach area, consisting of three spillover channels, is present in the eastern part of the crater rim. These channels connect the Liberta crater to the eastward portion of the valley system, continuing toward Moa Valles with a complex pattern of anabranching channels that is more than 180-km-long. Our crater counting results and hydrological calculations of infilling and spillover discharges of the Liberta crater-lake suggest that the system is the result of an Early Amazonian water-rich environment that was likely sustained by relatively short fluvial events (<102 years), thereby supporting the hypotheses that water-related erosion might have been active on Mars (at least locally) during the Amazonian. The most important water source for the system could

This thesis presents a structural analysis and phonon transparency investigation of the Ge-Au-Ge eutectic bond interface. Interface development was intended to maximize the interfacial ballistic phonon transparency to enhance the detection of the dark matter candidate WIMPs. The process which was developed provides an interface which produces minimal stress, low amounts of impurities, and insures Ge lattice continuity through the interface. For initial Au thicknesses of greater than 1,000 {angstrom} Au per substrate side, eutectic epitaxial growth resulted in a Au dendritic structure with 95% cross sectional and 90% planar Au interfacial area coverages. In sections in which Ge bridged the interface, lattice continuity across the interface was apparent. Epitaxial solidification of the eutectic interface with initial Au thicknesses < 500 A per substrate side produced Au agglomerations thereby reducing the Au planar interfacial area coverage to as little as 30%. The mechanism for Au coalescence was attributed to lateral diffusion of Ge and Au in the liquid phase during solidification. Phonon transmission studies were performed on eutectic interfaces with initial Au thicknesses of 1,000 {angstrom}, 500 {angstrom}, and 300 {angstrom} per substrate side. Phonon imaging of eutectically bonded samples with initial Au thicknesses of 300 {angstrom}/side revealed reproducible interfacial percent phonon transmissions from 60% to 70%. Line scan phonon imaging verified the results. Phonon propagation TOF spectra distinctly showed the predominant phonon propagation mode was ballistic. This was substantiated by phonon focusing effects apparent in the phonon imaging data. The degree of interface transparency to phonons and resulting phonon propagation modes correlate with the structure of the interface following eutectic solidification. Structural studies of samples with initial Au thickness of 1,000 {angstrom}/side appear to correspond with the phonon transmission study.

Eutectic solvent can solubilize high amount of some therapeutic compounds. Volatile eutectic solvent is interesting to be used as solvent in the preparation of nanosuspension with emulsion solvent evaporation technique. The mechanism of transformation from the eutectic emulsion to nanosuspension was investigated in this study. The 30% w/w ibuprofen eutectic solution was used as the internal phase, and the external phase is composed of Tween 80 as emulsifier. Ibuprofen nanosuspension was prepared by eutectic emulsion solvent evaporating method followed with ultrasonication. During evaporation process, the ibuprofen concentration in emulsion droplets was increased leading to a drug supersaturation but did not immediately recrystallize because of low glass transition temperature (Tg) of ibuprofen. The contact angle of the internal phase on ibuprofen was apparently lower than that of the external phase at all times of evaporation, indicating that the ibuprofen crystals were preferentially wetted by the internal phase than the external phase. From calculated dewetting value ibuprofen crystallization occurred in the droplet. Crystallization of the drug was initiated with external mechanical force, and the particle size of the drug was larger due to Ostwald ripening. Cavitation force from ultrasonication minimized the ibuprofen crystals to the nanoscale. Particle size and zeta potential of formulated ibuprofen nanosuspension were 330.87±51.49 nm and −31.1±1.6 mV, respectively, and exhibited a fast dissolution. Therefore, the combination of eutectic emulsion solvent evaporation method with ultrasonication was favorable for fabricating an ibuprofen nanosuspension, and the transformation mechanism was attained successfully. PMID:27366064

Eutectic solvent can solubilize high amount of some therapeutic compounds. Volatile eutectic solvent is interesting to be used as solvent in the preparation of nanosuspension with emulsion solvent evaporation technique. The mechanism of transformation from the eutectic emulsion to nanosuspension was investigated in this study. The 30% w/w ibuprofen eutectic solution was used as the internal phase, and the external phase is composed of Tween 80 as emulsifier. Ibuprofen nanosuspension was prepared by eutectic emulsion solvent evaporating method followed with ultrasonication. During evaporation process, the ibuprofen concentration in emulsion droplets was increased leading to a drug supersaturation but did not immediately recrystallize because of low glass transition temperature (T g) of ibuprofen. The contact angle of the internal phase on ibuprofen was apparently lower than that of the external phase at all times of evaporation, indicating that the ibuprofen crystals were preferentially wetted by the internal phase than the external phase. From calculated dewetting value ibuprofen crystallization occurred in the droplet. Crystallization of the drug was initiated with external mechanical force, and the particle size of the drug was larger due to Ostwald ripening. Cavitation force from ultrasonication minimized the ibuprofen crystals to the nanoscale. Particle size and zeta potential of formulated ibuprofen nanosuspension were 330.87±51.49 nm and -31.1±1.6 mV, respectively, and exhibited a fast dissolution. Therefore, the combination of eutectic emulsion solvent evaporation method with ultrasonication was favorable for fabricating an ibuprofen nanosuspension, and the transformation mechanism was attained successfully. PMID:27366064

To evaluate the reliability of metal-carbon eutectic systems as fixed points for the next generation of high-temperature standards the effect of thermodynamic properties related to the shape of eutectic phase diagram on the freezing temperature is investigated within the context of the numerical multi-phase-field model. The partition coefficient and liquidus slopes of the two solids involved in the eutectic reaction are varied deliberately and independently. The difference between the eutectic temperature and the freezing temperature is determined in dependence of the solid/liquid (s/l) interface shape and concentration. Where appropriate reference is made to the Jackson-Hunt analytical theory. It is shown that there are mainly two typical conditions to decrease the undercooling: 1) a small liquidus slope and 2) the associated difference between the eutectic composition and the liquid composition during solidification.

Eu doped CaF2/Li3AlF6 eutectics were grown by μ-PD method. The directionally solidified eutectic with well-aligned 600 nm diameter Eu:CaF2 scintillator fibers surrounded with Li3AlF6 was prepared. The grown eutectics showed an emission peak at 422 nm ascribed to Eu2+ 4f-5d transition from Eu:CaF2 scintillation fiber. Li concentration in the Eu:CaF2-Li3AlF6 eutectic is around 0.038 mol/cm3,which is two times higher than that of LiCaAlF6 single crystal (0.016 mol/cm3). The light yield of Eu:CaF2-Li3AlF6 eutectic was around 7000 ph/neutron. The decay time was about 550 ns (89%) and 1450 ns (11%).

The Zr-Cu-Al bulk glassy (BG) alloy, which has amorphous structure, possesses various properties such as high strength and toughness with compositional dependence. In the present study, density, positron annihilation lifetime and coincidence Doppler Broadening measurement have been performed for various compositional hyper-eutectic Zr-Cu-Al BG alloys. The density of hyper-eutectic Zr-Cu-Al BG alloys increases with decreasing of Zr fraction. In contrast, positron lifetime for all compositional alloys is almost constant about 165 psec. In addition, the CDB ratio profile is almost the same for hyper-eutectic alloys. This unchanging trend of CDB ratio profile is quite different from that of hypo-eutectic BG alloys. These results reveal that different internal structure exists in hyper and hypo-eutectic BG alloys.

The effects of gravity on the microstructure of directionally solidified near-eutectic cast irons are studied, using a Bridgman-type automatic directional solidification furnace aboard a NASA KC-135 aircraft which flies parabolic arcs and generates alternating periods of low-g (0.01 to 0.001 g, 30 seconds long) and high-g (1.8 g, 1.5 minutes long). Results show a refinement of the interlamellar spacing of the eutectic during low-g processing of metastable Fe-C eutectic alloys. Low-g processing of stable Fe-C-Si eutectic alloys (lamellar or spheroidal graphic) results in a coarsening of the eutectic grain structure. Secondary dendrite arm spacing of austenite increases in low-g and decreases in high-g. The effectiveness of low-gravity in the removal of buoyancy-driven graphite phase segregation is demonstrated.

In recent years, ionic liquids and deep eutectic mixtures have demonstrated great potential in extraction processes relevant to several scientific and technological activities. This review focuses on the applicability of these sustainable solvents in a variety of extraction techniques, including but not limited to liquid- and solid-phase (micro) extraction, microwave-assisted extraction, ultrasound-assisted extraction and pressurized liquid extraction. Selected applications of ionic liquids and deep eutectic mixtures on analytical method development, removal of environmental pollutants, selective isolation, and recovery of target compounds, purification of fuels, and azeotrope breaking are described and discussed. PMID:24811900

Eutectic alloys of Bi-Mn were directionally solidified using the Bridgman-Stockbarger technique to determine the influences of gravitationally-driven thermo-solutal convection on the Bi-MnBi rod eutectic. Experiments were conducted that varied the level of convection by varying the growth parameters and growth orientation, by microgravity damping, by applied magnetic field damping, and by imposing forced convection. Peltier interface demarcation and in situ thermocouple measurements were used to monitor interface velocity and thermal gradient and to evaluate interface planarity.

In this present work, we report numerical results of iron (cladding) corrosion study in interaction with lead-bismuth eutectic coolant of advanced nuclear reactors. The goal of this work is to study how the oxygen can be used to reduce the corrosion rate of cladding. The molecular dynamics method was applied to simulate corrosion process. By evaluating the diffusion coefficients, RDF functions, MSD curves of the iron and also observed the crystal structure of iron before and after oxygen injection to the coolant then we concluded that a significant and effective reduction can be achieved by issuing about 2% number of oxygen atoms to lead-bismuth eutectic coolant.

The tribological properties of a hardened steel U8-composite pair in contact in which bronze is used as the matrix and eutectic alloy powder (steel 30 Kh13 with 15 wt.% VC of eutectic structure) is used as a filler are studied under conditions of reciprocal sliding friction without lubrication. Composite and counterbody wear is not uniform and depends on the amount of filler within the range 20-80%. A composite with 80% filler has good tribological properties and satisfactory lathe machining.

The praseodymium and neodymium solubilities in the gallium-tin eutectic melt were measured for the first time in a temperature range of 423-1073 K using a high-temperature sampling technique. The data on the activity and solubility are used to calculate the activity coefficients, the excessive thermodynamic characteristics of α-praseodymium and α-neodymium in the Ga-Sn eutectic melts, and the separation factor for the Pr/Nd pair on gallium-tin electrodes in chloride melts.

This paper presents the electrical and morphological properties at the interface between a metal (Au) and a semiconductor (Si) formed by a novel transfer-printing technology. This work shows that a transfer-printed thin (hundreds of nanometers) Au film forms excellent electrical contact on a Si substrate when appropriate thermal treatment is applied. The successful electrical contact is attributed to eutectic joining, which allows for the right amount of atomic level mass transport between Au and Si. The outcomes suggest that transfer-printing-based micromanufacturing can realize not only strong mechanical bonding but also high-quality electrical contact via eutectic joining. PMID:23751269

The microscopic orientations of Ni-18.7 at.% Sn eutectics solidified from undercooled states, in particular, within an individual eutectic colony and among neighboring eutectic colonies, have been measured with respect to the eutectic Ni{sub 3}Sn and Ni phases; this was done using a scanning electron microscope equipped with the electron backscatter diffraction pattern (EBSP) mapping technique. The EBSPs and inverse pole figures indicate that the Ni{sub 3}Sn intermetallic compound is continuous and well oriented whereas the Ni solid solution is discontinuous and randomly oriented within an anomalous eutectic grain. Further examination reveals that although Ni particulates are random from an overall view, most neighboring Ni grains have small misorientations of less than 10 deg . The specific solidification sequence and the effect of released crystallization heat on subsequent crystallization are further considered, which enables the primary Ni phase to segment into individual grains whereas Ni{sub 3}Sn does not due to higher entropy of fusion. A little rotation or floating within the constrained framework of the crystallizing Ni{sub 3}Sn compound may yield small misorientation angles. The discontinuous Ni particulates and continuous Ni{sub 3}Sn network are of great significance in revealing the anomalous eutectic formation. The orientation among independent eutectic colonies is random owing to the random appearance of nuclei throughout the volume of undercooled melts. The macrotextures of pole figures (PFs) of two eutectic phases are also mapped versus melt undercooling, which can be interpreted well when considering the nucleation frequency, variation of eutectic colony size, microtexture within a single eutectic colony, and the overall microstructure evolution as a function of melt undercooling.

We develop a new method to measure source proper motions in microlensing events, which can partially overcome problems due to blending. It takes advantage of the fact that the source position is known precisely from the microlensing event itself. We apply this method to the event MOA-2011-BLG-262, which has a short timescale t E = 3.8 day, a companion mass ratio q = 4.7 × 10-3, and a very high or high lens-source relative proper motion μrel = 20 mas yr-1 or 12 mas yr-1 (for two possible models). These three characteristics imply that the lens could be a brown dwarf or a massive planet with a roughly Earth-mass "moon." The probability of such an interpretation would be greatly increased if it could be shown that the high lens-source relative proper motion was primarily due to the lens rather than the source. Based on the long-term monitoring data of the Galactic bulge from the Optical Gravitational Lensing Experiment, we measure the source proper motion that is small, {\\boldsymbol {\\mu }}_s = (-2.3, -0.9)+/- (2.8,2.6)\\,mas\\:yr^{-1} in a (north, east) Galactic coordinate frame. These values are then important input into a Bayesian analysis of the event presented in a companion paper by Bennett et al. Based on observations obtained with the 1.3 m Warsaw telescope at the Las Campanas Observatory of the Carnegie Institution for Science.

We report the result of the analysis of a dramatic repeating gravitational microlensing event OGLE-2009-BLG-092/MOA-2009-BLG-137, for which the light curve is characterized by two distinct peaks with perturbations near both peaks. We find that the event is produced by the passage of the source trajectory over the central perturbation regions associated with the individual components of a wide-separation binary. The event is special in the sense that the second perturbation, occurring {approx}100 days after the first, was predicted by the real-time analysis conducted after the first peak, demonstrating that real-time modeling can be routinely done for binary and planetary events. With the data obtained from follow-up observations covering the second peak, we are able to uniquely determine the physical parameters of the lens system. We find that the event occurred on a bulge clump giant and it was produced by a binary lens composed of a K- and M-type main-sequence stars. The estimated masses of the binary components are M{sub 1} = 0.69 {+-} 0.11 M{sub sun} and M{sub 2} = 0.36 {+-} 0.06 M{sub sun}, respectively, and they are separated in projection by r{sub perpendicular} = 10.9 {+-} 1.3 AU. The measured distance to the lens is D{sub L} = 5.6 {+-} 0.7 kpc. We also detect the orbital motion of the lens system.

We develop a new method to measure source proper motions in microlensing events, which can partially overcome problems due to blending. It takes advantage of the fact that the source position is known precisely from the microlensing event itself. We apply this method to the event MOA-2011-BLG-262, which has a short timescale t {sub E} = 3.8 day, a companion mass ratio q = 4.7 × 10{sup –3}, and a very high or high lens-source relative proper motion μ{sub rel} = 20 mas yr{sup –1} or 12 mas yr{sup –1} (for two possible models). These three characteristics imply that the lens could be a brown dwarf or a massive planet with a roughly Earth-mass 'moon'. The probability of such an interpretation would be greatly increased if it could be shown that the high lens-source relative proper motion was primarily due to the lens rather than the source. Based on the long-term monitoring data of the Galactic bulge from the Optical Gravitational Lensing Experiment, we measure the source proper motion that is small, μ{sub s}=(−2.3,−0.9)±(2.8,2.6) mas yr{sup −1} in a (north, east) Galactic coordinate frame. These values are then important input into a Bayesian analysis of the event presented in a companion paper by Bennett et al.

Developing and characterizing green solvents with low toxicity and cost is one of the most important issues in chemistry. Deep Eutectic Solvents (DESs), in this regard, have shown tremendous promise. Compared to popular organic solvents, DESs possess negligible VOCs and are non-flammable. Compared to ionic liquids, which share many characteristics but are ionic compounds and not ionic mixtures, DESs are cheaper to make, much less toxic and mostly biodegradable. An estimate of the polarity associated with DESs is essential if they are to be used as green alternatives to common organic solvents in industries and academia. As no one physical parameter can satisfactorily represent solute-solvent interactions within a medium, polarity of DESs is assessed through solvatochromic optical spectroscopic responses of several UV-vis absorbance and molecular fluorescence probes. Information on the local microenvironment (i.e., the cybotactic region) that surrounds several solvatochromic probes [betaine dye, pyrene, pyrene-1-carboxaldehyde, 1-anilino-8-naphthalene sulfonate (ANS), p-toluidinyl-6-naphthalene sulfonate (TNS), 6-propionyl-2-(dimethylaminonaphthalene) (PRODAN), coumarin-153, and Nile Red] for four common and popular DESs formed from choline chloride combined with 1,2-ethanediol, glycerol, urea, and malonic acid, respectively, in 1 : 2 molar ratios termed ethaline, glyceline, reline, and maline is obtained and used to assess the effective polarity afforded by each of these DESs. The four DESs as indicated by these probe responses are found to be fairly dipolar in nature. Absorbance probe betaine dye and fluorescence probes ANS, TNS, PRODAN, coumarin-153, and Nile Red, whose solvatochromic responses are based on photoinduced charge-transfer, imply ethaline and glyceline, DESs formed using alcohol-based H-bond donors, to be relatively more dipolar in nature as compared to reline and maline. The pyrene polarity scale, which is based on polarity-induced changes in

The eutectic properties of binary mixtures of some nonsteroidal anti-inflammatory drugs (NSAIDs) with ibuprofen were studied using differential scanning calorimetry (DSC) and phase equilibrium diagrams. The melting points of selected NSAIDs were significantly depressed due to binary eutectic formation with ibuprofen. Ketoprofen and ibuprofen were selected to study the effect of eutectic formation on membrane permeation using Franz diffusion cells and snake skin as the model membrane. The presence of aqueous isopropyl alcohol (IPA) was necessary to completely transform the solid drugs into an oily state at ambient temperature. As much as the 99.6% of ibuprofen and the 88.8% of ketoprofen added were found in the oily phase of the two-phase liquid system formed when aqueous IPA was added to the eutectic mixture. Due to the high drug concentration in the oily phase, and maximum thermodynamic activity, the two-phase liquid system showed enhanced membrane permeation rates of ibuprofen (37.5 microg/cm2/hr) and ketoprofen (33.4 microg/cm2/hr) compared to other reference preparations used. PMID:15776808

Deep eutectic solvent (DES) is a new class of solvents typically formed by mixing choline chloride with hydrogen bond donors such as amines, acids, and alcohols. Most DES's are non-reactive with water, biodegradable, and have acceptable toxicity profiles. Urea-choline chloride and malonic acid-choline chloride eutectic systems were characterized using differential scanning calorimetry (DSC) and thermal microscopy. A potential new 2:1 urea-choline chloride cocrystal with a melting point of 25 degrees C was characterized at the eutectic composition. The formation of this cocrystal suggests that DES should not be universally explained by simple eutectic melting, and may be useful in guiding the search for new DES systems. The lack of nucleation of the malonic acid-choline chloride system prohibited the construction of a phase diagram for this system using DSC. We also investigated possible uses of DES in solubilizing poorly soluble compounds for enhanced bioavailability in early drug development such as toxicology studies. For five poorly soluble model compounds, solubility in DES is 5 to 22,000 folds more than that in water. Thus, DES can be a promising vehicle for increasing exposure of poorly soluble compounds in preclinical studies. PMID:19477257

A growing number of non-toxic and biodegradable deep eutectic solvents (DES) have been discovered in recent years. This group encompasses the solidified crystalline material 3-(2-aminopyrimidin-1-yl)propanoate (3-2AP), a primary ammonium cation that is a construct of a typical DES. Synthesis of 3-(2-aminopyrimidin-1-yl)propanoate by quarternerization of the amine in the aromatic ring creates a novel deep eutectic solvent. An additional alteration to the DES construct is observed with the formation of a zwitterion between the positively charged quartenary amine group and the negatively charged carboxylate counter ion. The molecular arrangement, or construct, of a deep eutectic solvent will determine both its structure and application in industry. This report describes the synthesis and characterization of an 80:20 urea/3-2AP eutectic mixture with a melting point of 50°C, nearly 120°C lower than the melting temperature of 3-2AP (172.5°C). A cytotoxicity profile for 3-2AP exposed to A549 bronchoaveolar carcinoma cells revealed an LD50 of 337.65 mug/ml.

Mechanochemical synthesis has been applied to the rapid synthesis of Deep Eutectic Solvents (DESs), including Reline 200 (choline chloride : urea, 1 : 2), in a continuous flow methodology by Twin Screw Extrusion (TSE). This gave products in higher purity and with Space Time Yields (STYs), four orders of magnitude greater than for batch methods. PMID:26911554

The Jackson and Hunt (JH) theory has been modified to relax the assumption of isothermal solid liquid interface used in their treatment. Based on the predictions of this modified theory, the traditional definitions of regular and irregular eutectics are revised. For regular eutectics, the new model identifies a range of spacing within the limits defined by the minimum undercooling of the a and beta phases. For the irregular Al-Si eutectic system, two different spacing selection mechanisms were identified: (1) for a particular growth rate, a nearly isothermal interface can be achieved at a unique minimum spacing lambda (sub t); (2) the average spacing (lambda (sub av) greater than lambda (sub t) is essentially dictated by the undercooling of the faceted phase. Based on the modified theoretical model, a semiempirical expression has been developed to account for the influence of the temperature gradient, which is dominant in the irregular Al-Si system. The behavior of the Fe-Fe3C eutectic is also discussed. The theoretical calculations have been found to be in good agreement with the published experimental measurements.

The Jackson and Hunt (JH) theory has been modified to relax the assumption of isothermal solid/liquid interface(SLI) used in their treatment. Based on the predictions of this modified theory the traditional definitions of regular and irregular eutectics are revised. For regular eutectics the new model identifies a range of spacing within the limits defined by the minimum undercooling of the alpha and beta phase. For the irregular Al-Si eutectic system two different spacing selection mechanisms were identified: a) for a particular growth rate, a nearly isothermal interface can be achieved at a unique minimum spacing lambda(sub I); b) the average spacing (lambda(sub av) greater than lambda(sub I)) is essentially dictated by the undercooling of the faceted phase. Based on the modified theoretical model a semiempirical expression has been developed to account for the influence of the temperature gradient, which is dominant in the irregular Al-Si system. The behavior of the Fe-Fe3C eutectic is also discussed The theoretical calculations have been found to be in good agreement with the published experimental measurements.

A natLiCl-BaCl2:Eu2+ eutectic scintillator was synthesized by the vertical Bridgman method aiming at the application of thermal neutron detection. The molar ratio of LiCl and BaCl2 was 75.1/24.9, which corresponds to the eutectic composition in the LiCl-BaCl2 system. The grown eutectic showed a periodic microstructure of BaCl2:Eu2+ and LiCl phases with 2-3 μm thickness. The α-particle induced radioluminescence spectrum of the scintillator showed an intense emission peak at 406 nm due to the Eu2+ 5d1→4f emission from the BaCl2:Eu2+ phase and an additional weak emission peak at 526 nm. The scintillation decay time was 412 ns. LiCl-BaCl2:Eu2+ eutectic samples exhibited non-correlated neutron detection efficiency and light yield as a function of crystal length, suggesting material non-uniformities within the boule. The relative light yield was equal to or greater than that of Nucsafe lithium glass. Gamma-ray exposures indicate that gamma/neutron threshold discrimination for higher energy gamma-rays will be limited.

A small palm-sized, reference spectrometer, mounted on a remote-controlled model helicopter is being developed and tested by the National Physical Laboratory (NPL) in conjunction with City University, London. The developed system will be used as a key element for field vicarious calibration of optical earth observation systems in the visible-near infrared (VNIR) region. The spectrometer is hand held, low weight, and uses a photodiode array. It has good stray light rejection and wide spectral coverage, allowing simultaneous measurements from 400 to 900 nm. The spectrometer is traceable to NPL’s primary standard cryogenic radiometer via a high-temperature metal-carbon eutectic fixed-point blackbody. Once the fixed-point temperature has been determined (using filter radiometry), the eutectic provides a high emissivity and high stability source of known spectral radiance over the emitted spectral range. All wavelength channels of the spectrometer can be calibrated simultaneously using the eutectic transition without the need for additional instrumentation. The spectrometer itself has been characterized for stray light performance and wavelength accuracy. Its long-term and transportation stability has been proven in an experiment that determined the “World’s Bluest Sky”—a process that involved 56 flights, covering 100,000 km in 72 days. This vicarious calibration methodology using a eutectic standard is presented alongside the preliminary results of an evaluation study of the spectrometer characteristics.

Directional solidification of eutectic alloys has been recognized as promising technique for producing in situ composite materials exhibiting balance of properties. Therefore, an in situ NiAl-V eutectic composite has been successfully directionally solidified using Bridgman technique. The mechanical behavior of the composite including fracture resistance, microhardness, and compressive properties at room and elevated temperatures was investigated. Damage evolution and fracture characteristics were also discussed. The obtained results indicate that the NiAl-V eutectic retains high yield strength up to 1073 K (800 °C), above which there is a rapid decrease in strength. Its yield strength is higher than that of binary NiAl and most of the NiAl-based eutectics. The exhibited fracture toughness of 28.5 MPa√m is the highest of all other NiAl-based systems investigated so far. The material exhibited brittle fracture behavior of transgranular type and all observations pointed out that the main fracture micromechanism was cleavage.

A formula for the free energy difference between the undercooled liquid phase and the stable solid phase is derived for off-eutectic binary alloys in which the equilibrium solid/liquid transition takes place over a certain temperature range. The free energy change is then evaluated numerically for a Bi-25 at. pct Cd alloy modeled as a sub-subregular solution.

Deep eutectic solvents (DES) as a new kind of green solvent were used for the first time to excellently extract phenolic compounds from model oil. It was also proved that DES could be used to extract other polar compounds from non-polar or weakly-polar solvents by liquid-phase microextraction. PMID:25144155

Iron released by steel corrosion was found to be a key impurity in reactions with dissolved oxygen in liquid lead-bismuth eutectic alloys. The iron-oxygen-magnetite equilibrium was characterized, allowing the quantification of phenomena that are important for long-term operation of lead-alloy based installations such as corrosion rate control and management of precipitates. PMID:27383127

A previous investigation indicated that combustion efficiency of low burning-rate propellants could be improved if the aluminum fuel was replaced by aluminum particles coated with a magnesium-aluminum eutectic alloy (ALCAL). The purpose of the present investigation was to evaluate the possibility of improving the combustion efficiency of these propellants by admixing the eutectic with the aluminum rather than coating the aluminum. Tests of three propellants similar in every respect except for the metal fuel were conducted in test motors with 4.54 kg (10 lbm) of propellant. The first propellant used aluminum fuel; the second contained aluminum admixed with magnesium-aluminum eutectic; the third used ALCAL. The test results show the the admixed fuel gave better low burning-rate combustion efficiency than the other two. The test results also showed that the ALCAL was deficient in that much, if not all, of the coating material could be found as the fine particles in a bimodal mix of aluminum and eutectic. The combustion efficiency of low burning-rate aluminized propellants can be significantly improved by mixing a small amount of magnesium-aluminum alloy with the aluminum fuel.

The forced-convection heat-transfer characteristics of lead-bismuth eutectic were experimentally investigated. Experimental values of Nusselt number for lead-bismuth fell considerably below predicted values. The addition of a wetting agent did not change the heat transfer characteristics.

The effects of combined additions of Ca and P on the eutectic Si in a series of high purity Al-5 wt pct Si alloys have been investigated with the entrained droplet technique and complementary sets of conventional castings. Differential scanning calorimetry (DSC) and thermal analysis were used to investigate the eutectic droplet undercooling and the recalescence undercooling, respectively. Optical microscopy, SEM, EPMA, and TEM were employed to characterize the resultant microstructures. It was found that 250 ppm Ca addition to Al-5Si wt pct alloys with higher P contents leads to a significant increase of the eutectic droplet undercooling. For low or moderate cooling rates, the TEM results underline that Ca additions do not promote Si twinning. Thus, a higher twin density cannot be expected in Ca containing Al-Si alloys after, e.g., sand casting. Consequently, a refinement of the eutectic Si from coarse flake-like to fine plate-like structure, rather than a modification of the eutectic Si to a fibrous morphology, was achieved. This strongly indicates that the main purpose of Ca additions is to counteract the coarsening effect of the eutectic Si imposed by higher P concentrations. Significant multiple Si twinning was observed in melt-spun condition; however, this can be attributed to the higher cooling rate. After DSC heating (slow cooling), most of Si twins disappeared. Thus, the well-accepted impurity-induced twinning mechanism may be not valid in the case of Ca addition. The possible refinement mechanisms were discussed in terms of nucleation and growth of eutectic Si. We propose that the pre-eutectic Al2Si2Ca phase and preferential formation of Ca3P2 deactivate impurity particles, most likely AlP, poisoning the nucleation sites for eutectic Si.

Developing new green solvents is one of the key subjects in Green Chemistry. Ionic liquids (ILs) and deep eutectic solvents, thus, have been paid great attention to replace current harsh organic solvents and have been applied to many chemical processing such as extraction and synthesis. However, current ionic liquids and deep eutectic solvents have still limitations to be applied to a real chemical industry due to toxicity against human and environment and high cost of ILs and solid state of most deep eutectic solvents at room temperature. Recently we discovered that many plant abundant primary metabolites changed their state from solid to liquid when they were mixed in proper ratio. This finding made us hypothesize that natural deep eutectic solvents (NADES) play a role as alternative media to water in living organisms and tested a wide range of natural products, which resulted in discovery of over 100 NADES from nature. In order to prove deep eutectic feature the interaction between the molecules was investigated by nuclear magnetic resonance spectroscopy. All the tested NADES show clear hydrogen bonding between components. As next step physical properties of NADES such as water activity, density, viscosity, polarity and thermal properties were measured as well as the effect of water on the physical properties. In the last stage the novel NADES were applied to the solubilization of wide range of biomolecules such as non-water soluble bioactive natural products, gluten, starch, and DNA. In most cases the solubility of the biomolecules evaluated in this study was greatly higher than water. Based on the results the novel NADES may be expected as potential green solvents at room temperature in diverse fields of chemistry. PMID:23427801

Temperature programming of gas chromatography (GC) separation columns accelerates the elution rate of chemical species through the column, increasing the speed of analysis, and hence making it a favorable technique to speedup separations in microfabricated GCs (micro-GC). Temperature-programmed separations would be preferred in an all-silicon micro-column compared to a silicon-Pyrex® micro-column given that the thermal conductivity and diffusivity of silicon is 2 orders of magnitude higher than Pyrex®. This paper demonstrates how to fabricate all-silicon micro-columns that can withstand the temperature cycling required for temperature-programmed separations. The columns were sealed using a novel bonding process where they were first bonded using a gold eutectic bond, then annealed at 1100 °C to allow gold diffusion into silicon and form what we call a gold diffusion eutectic bond. The gold diffusion eutectic-bonded micro-columns when examined using scanning electron microscopy (SEM), scanning acoustic microscopy (SAM) and blade insertion techniques showed bonding strength comparable to the previously reported anodic-bonded columns. Gas chromatography-based methane injections were also used as a novel way to investigate proper sealing between channels. A unique methane elution peak at various carrier gas inlet pressures demonstrated the suitability of gold diffusion eutectic-bonded channels as micro-GC columns. The application of gold diffusion eutectic-bonded all-silicon micro-columns to temperature-programmed separations (120 °C min-1) was demonstrated with the near-baseline separation of n-C6 to n-C12 alkanes in 35 s.

Using uniaxial compression creep experiments, we characterized the transient and steady state deformation behaviors of eutectic aggregates of system ice I and MgSO4 11H2O (MS11; meridianiite), which has significance because of its likely presence on moons of the outer solar system. Synthetic samples of eutectic liquid bulk composition, which produce eutectic colonies containing 0.35-0.50 volume fraction MS11, were tested as functions of colony size and lamellar spacing, temperature (230-250 K), and confining pressure (0.1 and 50 MPa) to strains ???0.2. Up to a differential stress of 6 MPa, the ice I-MS11 aggregates display an order of magnitude higher effective viscosity and higher stress sensitivity than do aggregates of pure polycrystalline ice at the same conditions. The creep data and associated microstructural observations demonstrate, however, that the aggregates are additionally more brittle than pure ice, approaching rate-independent plasticity that includes rupture of the hydrate phase at 6-8 MPa, depending on the scale of the microstructure. Microstructures of deformed samples reveal forms of semibrittle flow in which the hydrate phase fractures while the ice phase deforms plastically. Semibrittle flow in the icy shell of a planetary body would truncate the lithospheric strength envelope and thereby decrease the depth to the brittle-ductile transition by 55% and reduce the failure limit for compressional surface features from 10 to ???6 MPa. A constitutive equation that includes eutectic colony boundary sliding and intracolony flow is used to describe the steady state rheology of the eutectic aggregates. Copyright ?? 2011 by the American Geophysical Union.

In this paper, we present the simulation of the eutectic phase transitions in the Pt-C system, in terms of both freezing and melting, using the multi-phase-field model. The experimentally obtained heat-extraction and -injection rates associated with the induction of freezing and melting are converted into the corresponding rates for microstructure-scale simulations. In spite of the extreme differences in the volume fractions of the FCC-Pt-rich phase on the one hand and graphite (C) on the other, satisfactory results for the kinetics of solidification and melting have been obtained, involving reasonable offsets in temperature, inducing freezing and melting, with respect to the equilibrium eutectic temperature. For freezing in the simulations, the needle/rod-like morphology, as experimentally observed, was reproduced for different heat extraction rates. The seemingly anomalous peak characterizing the simulated freezing curves is ascribed to the speed up of the solidification process due to the curvature effect. Similarly, a peak is observed in the experimental freezing curves, also showing up more clearly with increasing freezing rates. Melting was simulated starting from a frozen structure produced by a freezing simulation. The simulations reproduce the experimental melting curves and, together with the simulated freezing curves, help to understand the phase transition of the Pt-C eutectic. Finally, the effect of metallic impurities was studied. As shown for Au, impurities affect the morphology of the eutectic structure, their impact increasing with the impurity content, i.e., they can act as modifiers of the structure, as earlier reported for irregular eutectics.

Using uniaxial compression creep experiments, we characterized the transient and steady state deformation behaviors of eutectic aggregates of system ice I and MgSO4 • 11H2O (MS11; meridianiite), which has significance because of its likely presence on moons of the outer solar system. Synthetic samples of eutectic liquid bulk composition, which produce eutectic colonies containing 0.35-0.50 volume fraction MS11, were tested as functions of colony size and lamellar spacing, temperature (230-250 K), and confining pressure (0.1 and 50 MPa) to strains ≤ 0.2. Up to a differential stress of 6 MPa, the ice I-MS11 aggregates display an order of magnitude higher effective viscosity and higher stress sensitivity than do aggregates of pure polycrystalline ice at the same conditions. The creep data and associated microstructural observations demonstrate, however, that the aggregates are additionally more brittle than pure ice, approaching rate-independent plasticity that includes rupture of the hydrate phase at 6-8 MPa, depending on the scale of the microstructure. Microstructures of deformed samples reveal forms of semibrittle flow in which the hydrate phase fractures while the ice phase deforms plastically. Semibrittle flow in the icy shell of a planetary body would truncate the lithospheric strength envelope and thereby decrease the depth to the brittle-ductile transition by 55% and reduce the failure limit for compressional surface features from 10 to ˜6 MPa. A constitutive equation that includes eutectic colony boundary sliding and intracolony flow is used to describe the steady state rheology of the eutectic aggregates.

The microstructure resulting from the final stages of solidification—commonly referred to as eutectic islands—has been analysed in detail for three nickel-base superalloys containing Re and Ru. Focused ion beam 3-D reconstruction and EBSD-analysis were used to clarify the origin of different eutectic structure types. One common type of parent 3-D eutectic structure was identified. The solidification process of the final solidifying liquid has been further investigated by electron probe microanalysis mappings along with DICTRA simulations. Two models for diffusion controlled phase transformations are shown to present a fair description of the solidification sequence.

Deep eutectic solvents (DESs) represent an alternative class of ionic fluids closely resembling room-temperature ionic liquids (RTILs), although, strictly speaking, they are distinguished by the fact that they also contain an organic molecular component (typically, a hydrogen bond donor like a urea, amide, acid, or polyol), frequently as the predominant constituent. Practically speaking, DESs are attractive alternatives to RTILs, sharing most of their remarkable qualities (e.g., tolerance to humidity, negligible vapor pressure, thermostability, wide electrochemical potential windows, tunability) while overcoming several limitations associated with their RTIL cousins. Particularly, DESs are typically, less expensive, more synthetically accessible (typically, from bulk commodity chemicals using solvent/waste-free processes), nontoxic, and biodegradable. In this Account, we provide an overview of DESs as designer solvents to create well-defined nanomaterials including shape-controlled nanoparticles, electrodeposited films, metal-organic frameworks, colloidal assemblies, hierarchically porous carbons, and DNA/RNA architectures. These breakthroughs illustrate how DESs can fulfill multiple roles in directing chemistry at the nanoscale: acting as supramolecular template, metal/carbon source, sacrificial agent (e.g., ammonia release from urea), and/or redox agent, all in the absence of formal stabilizing ligand (here, solvent and stabilizer are one and the same). The ability to tailor the physicochemical properties of DESs is central to controlling their interfacial behavior. The preorganized "supramolecular" nature of DESs provides a soft template to guide the formation of bimodal porous carbon networks or the evolution of electrodeposits. A number of essential parameters (viscosity, polarity, surface tension, hydrogen bonding), plus coordination with solutes/surfaces, all play significant roles in modulating species reactivity and mass transport properties governing the

In the framework of the Accelerator-Driven System (ADS), the Pb-Bi eutectic can be used as spallation target for neutron production. The Pb-Bi flow in contact with the ADS structural steels, T 91 (Fe-9Cr martensitic steel) and 316L (Fe-17Cr-10Ni austenitic steel), can dissolve the main steel components: iron, chromium and nickel. According to literature, in low oxygen containing Pb-Bi, the dissolution rates of 316L depend, at least, on the nickel solubility limit as it dissolves preferentially in the Pb-Bi alloy. Consequently, the determination of this physico-chemical data in the temperature range of the ADS operating conditions (350-450 °C) is needed for the prediction of the corrosion rates in ADS. The nickel solubility limit in Pb-Bi is available in the literature from 400 °C to 900 °C but not for lower temperatures. However, the Ni-Bi phase diagram leads one to suppose that the nickel solubility limit law changes for lower temperatures. Consequently in this study, two experimental techniques have been implemented for the determination of the nickel solubility limit at low temperatures. The first one is performed from 400 °C to 500 °C using the Laser Induce Breakdown Spectroscopy (LIBS). The LIBS technique permits to obtain in situ measurements directly performed on liquid Pb-Bi. This characteristic is very interesting as it allows to monitor on line the concentration of the dissolved impurities in the liquid coolant. However, this technique is still under development and optimization on liquid Pb-Bi medium. The second technique is ICP-AES. This technique, commonly used to analyze alloys composition, is interesting as it permits a global analysis of a Pb-Bi sample. Moreover, the measurement made by ICP-AES is very reliable, very accurate and optimized for such analyses. However, this technique is ex situ; this is its main disadvantage. Experiments using ICP-AES were performed from 350 °C to 535 °C. The two techniques lead to the same solubility limit in

Characterizing a microlensing planet is done by modeling an observed lensing light curve. In this process, it is often confronted that solutions of different lensing parameters result in similar light curves, causing difficulties in uniquely interpreting the lens system, and thus understanding the causes of different types of degeneracy is important. In this work, we show that incomplete coverage of a planetary perturbation can result in degenerate solutions even for events where the planetary signal is detected with a high level of statistical significance. We demonstrate the degeneracy for an actually observed event OGLE-2012-BLG-0455/MOA-2012-BLG-206. The peak of this high-magnification event (A {sub max} ∼ 400) exhibits very strong deviation from a point-lens model with Δχ{sup 2} ≳ 4000 for data sets with a total of 6963 measurements. From detailed modeling of the light curve, we find that the deviation can be explained by four distinct solutions, i.e., two very different sets of solutions, each with a twofold degeneracy. While the twofold (so-called close/wide) degeneracy is well understood, the degeneracy between the radically different solutions is not previously known. The model light curves of this degeneracy differ substantially in the parts that were not covered by observation, indicating that the degeneracy is caused by the incomplete coverage of the perturbation. It is expected that the frequency of the degeneracy introduced in this work will be greatly reduced with the improvement of the current lensing survey and follow-up experiments and the advent of new surveys.

We present the first microlensing candidate for a free-floating exoplanet-exomoon system, MOA-2011-BLG-262, with a primary lens mass of M host ~ 4 Jupiter masses hosting a sub-Earth mass moon. The argument for an exomoon hinges on the system being relatively close to the Sun. The data constrain the product ML πrel where ML is the lens system mass and πrel is the lens-source relative parallax. If the lens system is nearby (large πrel), then ML is small (a few Jupiter masses) and the companion is a sub-Earth-mass exomoon. The best-fit solution has a large lens-source relative proper motion, μrel = 19.6 ± 1.6 mas yr-1, which would rule out a distant lens system unless the source star has an unusually high proper motion. However, data from the OGLE collaboration nearly rule out a high source proper motion, so the exoplanet+exomoon model is the favored interpretation for the best fit model. However, there is an alternate solution that has a lower proper motion and fits the data almost as well. This solution is compatible with a distant (so stellar) host. A Bayesian analysis does not favor the exoplanet+exomoon interpretation, so Occam's razor favors a lens system in the bulge with host and companion masses of M_host = 0.12^{+0.19}_{ -0.06}\\,M_\\odot and m_comp = 18^{+28}_{ -10}\\,{M_\\oplus }, at a projected separation of a_\\perp = 0.84^{+0.25}_{ -0.14} AU. The existence of this degeneracy is an unlucky accident, so current microlensing experiments are in principle sensitive to exomoons. In some circumstances, it will be possible to definitively establish the mass of such lens systems through the microlensing parallax effect. Future experiments will be sensitive to less extreme exomoons.

Microlensing detections of cool planets are important for the construction of an unbiased sample to estimate the frequency of planets beyond the snow line, which is where giant planets are thought to form according to the core accretion theory of planet formation. In this paper, we report the discovery of a giant planet detected from the analysis of the light curve of a high-magnification microlensing event MOA 2010-BLG-477. The measured planet-star mass ratio is q = (2.181 {+-} 0.004) Multiplication-Sign 10{sup -3} and the projected separation is s = 1.1228 {+-} 0.0006 in units of the Einstein radius. The angular Einstein radius is unusually large {theta}{sub E} = 1.38 {+-} 0.11 mas. Combining this measurement with constraints on the 'microlens parallax' and the lens flux, we can only limit the host mass to the range 0.13 < M/M{sub Sun} < 1.0. In this particular case, the strong degeneracy between microlensing parallax and planet orbital motion prevents us from measuring more accurate host and planet masses. However, we find that adding Bayesian priors from two effects (Galactic model and Keplerian orbit) each independently favors the upper end of this mass range, yielding star and planet masses of M{sub *} = 0.67{sup +0.33}{sub -0.13} M{sub Sun} and m{sub p} = 1.5{sup +0.8}{sub -0.3} M{sub JUP} at a distance of D = 2.3 {+-} 0.6 kpc, and with a semi-major axis of a = 2{sup +3}{sub -1} AU. Finally, we show that the lens mass can be determined from future high-resolution near-IR adaptive optics observations independently from two effects, photometric and astrometric.

The presence of pesticide residues in fruit is a serious health concern. This paper for the first time demonstrated the Hazard Index (HI) method to carry out acute, chronic and cumulative health risk assessment to the 14 groups of insecticides for three subpopulations. The challenge of this study was to present results from a long period of research (years 2005-2014) with toxicological aspects, especially in multiresidue samples. Near 1000 fresh pome, stone, berries and small fruit were prepared by two accredited MSPD and QuEChERS methods followed by liquid and gas chromatography analyses with various systems of detection ECD/NPD/MS/MS. Twenty percent of the fruit samples contained 16 insecticide residues in the range of 0.01-0.81mg/kg and 3% over MRL. The class of pesticide with the highest contribution to the ADI was found to be OPPs: dimethoate and diazinon for adults 48% and 66% of the ADI whereas for infants 144% and 294% of the ADI. The highest contributions of the cHQ to common MoA pesticides were AChE inhibitors: 135% for adults and 528% for infants, sodium channel modulators 4.9% and 20%, nicotic acetylocholine receptor <2.9% and <10.6% for adults and infants, respectively. The fruit with the highest contribution to the ADI were found to be apples (316%, 58%), cherries (96%, 37%) and pears (129%, 33%) for infants and adults. The study findings indicated that dietary exposures to insecticide residues in fruit would be unlikely to pose unacceptable health risks for the infants, toddlers and adults. PMID:27220092

Geometrical thermodynamics is used to analyze the possible dependences of the Gibbs energy on temperature and component concentration in the two-phase region during nonequilibrium solidification of eutectic alloys.

In situ composite materials obtained by directional growth of eutectic alloys usually show improved properties, that make them potential candidates for high temperature applications. The eutectic alloy found in the Al-Nb system is composed of the two intermetallic phases Al{sub 3}Nb (D0{sub 22}) and Nb{sub 2}Al (D8{sub b}). This paper describes the directional solidification of an Al-Nb eutectic alloy using a Bridgman type facility at growth rates varying from 1.0 to 2.9 cm/h. Longitudinal and transverse sections of grown samples were characterized regarding the solidification microstructure by using optical and scanning electron microscopy, energy dispersive spectroscopy (EDS) and X-ray diffraction. Despite both phases being intermetallic compounds, the eutectic microstructure obtained was very regular. The results obtained were discussed regarding the effect of the growth rate on the microstructure, lamellar-rod transition and variation of phase volume fraction.

Serial sectioning methods continue to produce an abundant amount of image data for quantifying the three-dimensional nature of material microstructures. Here, we discuss a methodology to automate detecting and characterizing eutectic particles taken from serial images of a production turbine blade made of a heat-treated single crystal Ni-based superalloy (PWA 1484). This method includes two important steps for unassisted eutectic particle characterization: automatically identifying a seed point within each particle and segmenting the particle using a region growing algorithm with an automated stop point. Once detected, the segmented eutectic particles are used to calculate microstructural statistics for characterizing and reconstructing statistically representative synthetic microstructures for single crystal Ni-based superalloys. The significance of this work is its ability to automate characterization for analysing the 3D nature of eutectic particles.

Near-eutectic Sn-Ag-Cu (SAC) solders are currently considered as major lead-free replacement candidates for Sn-Pb eutectic alloys in microelectronics applications. In this thesis, the microstructural thermal stability including recrystallization, grain growth behavior, Pb and Au contamination effects and interaction of the SAC solder with Cu and Ni substrates were investigated. The true eutectic composition of the Sn-Ag-Cu alloy was verified to be Sn3.5Ag0.9Cu wt.%, and the eutectic melting temperature was determined to be 217.4 +/- 0.8°C. The system was classified as belonging to faceting (Cu6Sn5)-faceting (Ag3Sn)-nonfaceting (Sn matrix) ternary eutectic. The most significant consequence of Pb contamination was the formation of a quaternary eutectic phase (Sn-Ag-Cu-Pb) with a melting point at 176°C. Similarly, the presence of gold in the SAC alloy led to a development of a new quaternary phase (Sn-Ag-Cu-Au) melting at 204°C. Prolonged aging of SAC-4 wt.% Au on nickel resulted in the deposition of a new, previously unreported, intermetallic (IMC) layer, ((Au1-xCUx)6Sn 5, 15 wt.% of Au) on top of the existing (Cu1-yNi y)6Sn5 layer. The interfacial products that formed during soldering to copper were Cu6Sn5 and Cu3Sn. Soldering to nickel resulted in the formation of one layer, (Cu1-yNiy) 6Sn5, which was different from the expected Ni3Sn 4 layer. A small copper content in the SAC solder (0.7 wt.%) was sufficient to promote this thermodynamic shift. Intermetallic growth on Cu during solid state aging was established to be bulk diffusion controlled. The IMC layers in the SAC system grew at a slower rate than in the Sn-Pb system. It was found that the reliability of SAC solder joints on copper was considerably better than on nickel due to copper enrichment during reflow and subsequent Cu6Sn5 intermetallic precipitation. Enhanced copper and silver diffusion followed by tin recrystallization and grain growth, cavity nucleation and subsequent micro-crack linkage formed

The heterogeneous nucleation of primary Si and eutectic Si can be attributed to the presence of AlP. Although P, in the form of AlP particles, is usually observed in the centre of primary Si, there is still a lack of detailed investigations on the distribution of P within primary Si and eutectic Si in hypereutectic Al-Si alloys at the atomic scale. Here, we report an atomic-scale experimental investigation on the distribution of P in hypereutectic Al-Si alloys. P, in the form of AlP particles, was observed in the centre of primary Si. However, no significant amount of P was detected within primary Si, eutectic Si and the Al matrix. Instead, P was observed at the interface between the Al matrix and eutectic Si, strongly indicating that P, in the form of AlP particles (or AlP ‘patch’ dependent on the P concentration), may have nucleated on the surface of the Al matrix and thereby enhanced the heterogeneous nucleation of eutectic Si. The present investigation reveals some novel insights into heterogeneous nucleation of primary Si and eutectic Si by AlP in hypereutectic Al-Si alloys and can be used to further develop heterogeneous nucleation mechanisms based on adsorption. PMID:27120994

In the present study, a eutectic platform was designed as an in situ cross-linked eutectic tablet for structural protection, enhanced intestinal permeation, and controlled release of proteins after oral administration. Physicochemical and physicomechanical analyses of the eutectic tablets were undertaken to elucidate the in situ cross-linking mechanism, thermal transitions, crystallinity, ex vivo permeation, and in vitro release of the protein. Following thermal characterization, results revealed successful eutectic formation with a melting point to 37°C. Protein release from the formulation was controlled over 24 h with a maximum fractional release of ±0.8 for all formulations. The release pattern alternated between phases of burst and slow release which was attributed to the combined effects of swelling, surface erosion, and in situ cross-linking. Mathematical modeling of the protein release kinetics corresponded best with the Higuichi model with near zero-order (R(2) ≈ 0.9787) release. The permeation-enhancing effect of menthol contained within the eutectic powder blend was investigated and results showed an enhanced protein flux (0.0576-0.0720 mg·cm(-2) h(-1)) across the intestinal tissue model compared with a control formulation. Extensive in vitro characterization highlighted the successful design of the eutectic tablets as a potential oral delivery system for proteins with structural protection, enhanced intestinal permeation, and controlled release. PMID:27262202

The heterogeneous nucleation of primary Si and eutectic Si can be attributed to the presence of AlP. Although P, in the form of AlP particles, is usually observed in the centre of primary Si, there is still a lack of detailed investigations on the distribution of P within primary Si and eutectic Si in hypereutectic Al-Si alloys at the atomic scale. Here, we report an atomic-scale experimental investigation on the distribution of P in hypereutectic Al-Si alloys. P, in the form of AlP particles, was observed in the centre of primary Si. However, no significant amount of P was detected within primary Si, eutectic Si and the Al matrix. Instead, P was observed at the interface between the Al matrix and eutectic Si, strongly indicating that P, in the form of AlP particles (or AlP 'patch' dependent on the P concentration), may have nucleated on the surface of the Al matrix and thereby enhanced the heterogeneous nucleation of eutectic Si. The present investigation reveals some novel insights into heterogeneous nucleation of primary Si and eutectic Si by AlP in hypereutectic Al-Si alloys and can be used to further develop heterogeneous nucleation mechanisms based on adsorption. PMID:27120994

Coating systems have been proposed for potential use on eutectic alloy components in high-temperature gas turbine engines. In a study to prevent the deterioration of such systems by diffusion, a tungsten sheet 25 microns thick was placed between eutectic alloys and an Ni-Cr-Al layer. Layered test specimens were aged at 1100 C for as long as 500 h. Without the tungsten barrier the delta phase of the eutectic deteriorated by diffusion of niobium into the Ni-Cr-Al. Insertion of the tungsten barrier stopped the diffusion of niobium from the delta phase. Chromium diffusion from the Ni-Cr-Al into the gamma/gamma-prime phase of the eutectic was greatly reduced by the barrier. However, the barrier thickness decreased with time, and tungsten diffused into both the Ni-Cr-Al and the eutectic. When the delta platelets were aligned parallel rather than perpendicular to the Ni-Cr-Al layer, diffusion into the eutectic was reduced.

In the non-aqueous reprocessing process of spent nuclear fuels by the pyro-electrochemical method, a spent fuel is dissolved into molten LiCl-KCl and NaCl-CsCl eutectics and dissolved uranium and plutonium are collected as either metal or oxide. However, the binary alkali chloride mixture with the lowest melting point is the LiCl-RbCl eutectic. In this study, electronic absorption spectra of U3+ and U4+ in molten LiCl-RbCl eutectic at various temperatures between 673 and 973 K were measured by the UV/Vis/NIR spectrophotometry. We confirmed that these spectra were similar to those in molten LiCl-KCl and NaCl-CsCl eutectics. The sensitive absorption bands of U4+ in LiCl-RbCl eutectic were found at 22000, 16500, 14900, 8600, and 4950 cm-1. The large absorption bands of U4+ over 25000 cm-1 increased with increasing melt temperature, while absorption peaks at 15500-4000 cm-1 decreased. The large absorption bands of U3+ in LiCl-RbCl eutectic were observed over 14000 cm-1. The sensitive absorption bands of U3+ at Vis/NIR region were found at 13300, 11500-11200, 9800-9400, and 8250 cm-1, and these peaks decreased with increasing temperature.

A ternary eutectic alloy with a composition of 57.2 pct Bi, 24.8 pct In, and 18 pct Sn was continuously cast into wire of 2 mm diameter with casting speeds of 14 and 79 mm/min using the Ohno Continuous Casting (OCC) process. The microstructures obtained were compared with those of statically cast specimens. Extensive segregation of massive Bi blocks, Bi complex structures, and tin-rich dendrites was found in specimens that were statically cast. Decomposition of {radical}Sn by a eutectoid reaction was confirmed based on microstructural evidence. Ternary eutectic alloy with a cooling rate of approximately 1 C/min formed a double binary eutectic. The double binary eutectic consisted of regions of BiIn and decomposed {radical}Sn in the form of a dendrite cell structure and regions of Bi and decomposed {radical}Sn in the form of a complex-regular cell. The Bi complex-regular cells, which are a ternary eutectic constituent, existed either along the boundaries of the BiIn-decomposed {radical}Sn dendrite cells or at the front of elongated dendrite cell structures. In the continuously cast wires, primary Sn dendrites coupled with a small Bi phase were uniformly distributed within the Bi-In alloy matrix. Neither massive Bi phase, Bi complex-regular cells, no BiIn eutectic dendrite cells were observed, resulting in a more uniform microstructure in contrast to the heavily segregated structures of the statically cast specimens.

The heterogeneous nucleation of primary Si and eutectic Si can be attributed to the presence of AlP. Although P, in the form of AlP particles, is usually observed in the centre of primary Si, there is still a lack of detailed investigations on the distribution of P within primary Si and eutectic Si in hypereutectic Al-Si alloys at the atomic scale. Here, we report an atomic-scale experimental investigation on the distribution of P in hypereutectic Al-Si alloys. P, in the form of AlP particles, was observed in the centre of primary Si. However, no significant amount of P was detected within primary Si, eutectic Si and the Al matrix. Instead, P was observed at the interface between the Al matrix and eutectic Si, strongly indicating that P, in the form of AlP particles (or AlP ‘patch’ dependent on the P concentration), may have nucleated on the surface of the Al matrix and thereby enhanced the heterogeneous nucleation of eutectic Si. The present investigation reveals some novel insights into heterogeneous nucleation of primary Si and eutectic Si by AlP in hypereutectic Al-Si alloys and can be used to further develop heterogeneous nucleation mechanisms based on adsorption.

A new bonding technique is proposed by using localized heating to supplythe bonding energy.Heating is achieved by applying a dc current through micromachined heaters made of gold which serves as both the heating and bonding material.At the interface of silicon and gold, the formation of eutectic bond takes place in about 5 minutes.Assembly of two substrates in microfabrication processescan be achieved by using this method.In this paper the following important results are obtained:1) Gold diffuses into silicon to form a strong eutectic bond by means of localized heating.2) The bonding strength reaches the fracture toughness of the bulk silicon.3) This bonding technique greatly simplifies device fabrication andassembly processes.

In recent years many studies into green solvents have been undertaken and deep eutectic solvents (DES) have emerged as sustainable and green alternatives to conventional solvents since they may be formed from cheap non-toxic organic precursors. In this study we examine amphiphile behaviour in these novel media to test our understanding of amphiphile self-assembly within environments that have an intermediate polarity between polar and non-polar extremes. We have built on our recently published results to present a more detailed structural characterisation of micelles of sodium dodecylsulfate (SDS) within the eutectic mixture of choline chloride and urea. Here we show that SDS adopts an unusual cylindrical aggregate morphology, unlike that seen in water and other polar solvents. A new morphology transition to shorter aggregates was found with increasing concentration. The self-assembly of SDS was also investigated in the presence of water; which promotes the formation of shorter aggregates. PMID:27157993

The Space Shuttle Columbia carried an Alloy Undercooling Experiment on its STS 61-C mission in January, 1986. The experiment was performed in an electromagnetic levitator. A sample of Ni-32.5 wt pct Sn eutectic was melted and solidified under microgravity conditions in the Space Shuttle. The specimen achieved only a fairly small undercooling, probably less than 30 K. The specimen was examined by optical and scanning electron microscopy. The surface and cross-sectional microstructures were primarily composed of normal lamellar eutectic, but showed several interesting features, including an apparent surface nucleation site, curved dendrites with nonorthogonal secondary arms, dendrite fragments with extremely fine arm spacing, submicron precipitates, and faceted crystals. The results of the space experiment are presented and compared with ground-based results obtained with the same alloy.

Recent improvements in the resolution of the X-ray Transmission Microscope (XTM) for Solidification Studies provide microstructure feature detectability down to 5 micrometers during solidification. This presentation will show the recent results from observations made in real-time of the solid-liquid interfacial morphologies of the Al-CuAI2 eutectic alloy. Lamellar dimensions and spacings, transitions of morphology caused by growth rate changes, and eutectic grain structures are open to measurements. A unique vantage point viewing the face of the interface isotherm is possible for the first time with the XTM due to its infinite depth of field. A video of the solid-liquid interfaces seen in-situ and in real-time will be shown.

We present a eutectic Phase-Field Model for a Mo-Si-B alloy at ternary eutectic composition (Mo-17.5Si-8B), under a constant thermal gradient. The process parameters like cooling rate and thermal gradient were obtained directly from the experimental procedure of zone melting. The equilibrium interface geometries and interface mobility were calculated using an isotropic model. The phase equilibria and the other thermodynamic parameters are obtained by linearizing the Mo-Si-B ternary phase diagram. We have investigated the effect of process parameters on the lamellar growth pattern and lamella pattern stability with respect to the Jackson-Hunt minimum undercooling spacing theory. In order to examine the generated results by the model, they were validated with experimental observed microstructures and measurements and showed to be in a good agreement with the experimental observations.

The (lambda-squared)(V) deviation for diffusion-only rod eutectic growth, where lambda is the interrod spacing and V is the growth velocity, was studied at growth velocities less than 5 cm/h in directionally solidified eutectic Bi-Mn (Bi/MnBi). At lower growth velocities, (V less than 0.5 cm/h) morphological instability occurred which resulted in nonaligned, irregularly dispersed MnBi fibers. The (lambda-squared)(V) relation was experimentally determined over a range of growth velocities between 0.1 and 50 cm/h, thermal gradients in the liquid at the liquid-solid interface that varied from 40 to 120 C/cm and solidification orientation with respect to the direction of gravity. Naturally induced, convective instabilities are suggested as a possible growth velocity limit for cooperative growth in the Bi-Mn and related alloy systems.

The ZrC-ZrB2, ZrC-TiB2, and TiC-TiB2 metal diboride-metal carbide pseudo-binary eutectic systems have been successfully solidified directionally by means of the floating zone method. The first and third of these eutectics possess a morphology consisting of columnar grains of parallel lamellae with interlamellar spacings that adhere to the lambda-squared (R) C relationship, while the second is noted to solidify in a Chinese calligraphy-like morphology of broken and deformed lamellae. This phenomenon may be related to solid solution effects, but it did not prevent the interlamellar spacings from following the aforementioned law. The calligraphic effect's values are larger than those of the other two systems, and the constant, C, is accordingly about an order of magnitude larger. All three of these cubic-hexagonal systems exhibited identical epitaxial relationships. 24 references.

Protective coatings required for the Ni-Nb-Cr-Al directionally solidified eutectic superalloy were developed and evaluated on the basis of oxidation resistance, diffusional stability, thermal fatigue, and creep resistance. NiCrAlY+Pt and NiCrAlY physical vapor-deposition coating systems exhibited the best combination of properties. Burner-rig testing indicated that the useful life of a 127-micron-thick NiCrAlY+Pt coating exceeds 1000 h at 1366 K. Eutectic-alloy creep lives at 1311 K and a stress of 151.7 MN/sq m were greater for NiCrAlY+Pt-coated specimens than for uncoated specimens by a factor of two.

Al2O3-YAG-ZrO2 eutectic ceramic plates 10 mm in width, 2.4 mm in thickness and 100 mm in length were directionally grown by micro-pulling down technique under different growth rate (0.1-1 mm/min). The effects of the solidification rate on the crystallographic orientation and microstructure properties were analyzed in considerable detail. The microstructure spacing λ depends on the pulling rate v following the law: λ = 7 . 2 v-1/2 where λ is in μm and v in μm/s. For low growth rate (v<0.25), the ternary eutectic plates had homogeneous and regular microstructures and higher pulling rate heterogeneity in the morphology corresponding to colonies presence. The annealed plates did not undergo chemical reaction but slight grain growth was observed.

The effect of solute gradient induced convection during vertical solidification on the macrosegregation of Pb-rich Pb-Sn off-eutectic alloys is determined experimentally as a function of composition and growth rate. In many cases macrosegregation is sufficient to prevent the plane front solidification of the alloy. The transition from dendritic to composite structure is found to occur when the composition of the solid is close enough to the eutectic composition to satisfy a stability criterion based on the ratio of the liquid temperature gradient to growth rate. A vertical or horizontal magnetic field of 0.1 T (1 kilogauss) does not reduce macrosegregation, but downward solidification (liquid below solid) virtually eliminates macrosegregation in small (3 mm) diameter samples.

The so-called crystallization courtyard is investigated that forms in processes of mass crystallization around the Ge and Si crystals and their solid solutions (Ge+Si) during cooling of hypereutectic alloys in the Ge-Al, Si-Al, and (Ge+Si)-Al eutectic systems. For the first time, data on the composition and microhardness of this crystallization courtyard are given and its role is shown as a stopper of cracking in an Al-(Ge,Si) system during rapid cooling after the heating system is turned off. For the first time, it is suggested that a crystallization courtyard forms in all hypereutectic systems (including every system in which the amount of the taken solvent does not correspond to the eutectic point).

The formation of high energy density, storage devices is achievable using composite material systems. Alternate layering of carbon aerogel wafers and Ni foils with rnicroporous separators is a prospective composite for capacitor applications. An inherent problem exists to form a physical bond between Ni and the porous carbon wafer. The bonding process must be limited to temperatures less than 1000{degrees}C, at which point the aerogel begins to degrade. The advantage of a low temperature eutectic in the Ni-Ti alloy system solves this problem. Ti, a carbide former, is readily adherent as a sputter deposited thin film onto the carbon wafer. A vacuum bonding process is then used to join the Ni foil and Ti coating through eutectic phase formation. The parameters required for successfld bonding are described along with a structural characterization of the Ni foil-carbon aerogel wafer interface.

We propose a model of equiaxed eutectic solidification that couples macroscopic heat diffusion with a microscopic description of nucleation and growth of the eutectic grains. The heat equation is solved numerically by means of an implicit finite difference method. The evolution of solid fraction is deduced from a stochastic model of nucleation and growth which uses the local temperature (interpolated from the FDM mesh) to determine the local grain density and the local growth rate. The model predicts the evaluations of both temperature and solid fraction at any point of the sample. Moreover, a realistic appearance of the recalescence on the cooling curves, as well as a detailed picture of the microstructure, are predicted. We apply the model to the solidification of grey cast iron.

The interface of a 1 : 2 molar choline chloride/ethylene glycol deep eutectic solvent with a glassy carbon electrode has been investigated by polarization modulation reflection-absorption spectroscopy (PM-IRRAS). Temporal spectral changes at open circuit potential show the experiments to be surface sensitive and indicate slow adsorption of electrolyte molecules on the electrode surface. In situ spectroelectrochemical PM-IRRAS measurements reveal characteristic potential-dependent changes of band intensities and wavenumber-shifts in the surface spectra. The potential dependent spectral changes are discussed in terms of adsorption, reduction, desorption and reorientation of choline cations at the interface. Analogies are drawn to the ionic layer structure proposed for the architecture of electrode/ionic liquid interfaces. The results show that in situ PM-IRRAS is generally applicable to glassy carbon electrodes and to electrode interfaces with deep eutectic solvents. PMID:25908481

Coating systems proposed for potential use on eutectic alloy components in high-temperature gas turbine engines were studied with emphasis on deterioration of such systems by diffusion. A 1-mil thick W sheet was placed between eutectic alloys and a NiCrAl layer. Layered test specimens were aged at 1100 C for as long as long as 500 hours. Without the W barrier, the delta phase of the eutectic deteriorated by diffusion of Nb into the NiCrAl. Insertion of the W barrier stopped the diffusion of Nb from delta. Chromium diffusion from the NiCrAl into the gamma/gamma prime phase of the eutectic was greatly reduced by the barrier. However, the barrier thickness decreased with time; and W diffused into both the NiCrAl and the eutectic. When the delta platelets were alined parallel to the NiCrAl layer, rather than perpendicular, diffusion into the eutectic was reduced.

Deep eutectic solvents (DESs), as a novel class of green solvents, were successfully applied as eco-friendly and sustainable reaction media for fast surface modification of spherical porous silica, resulting in stationary phases for high-performance liquid chromatography. The new reaction media were advantageous over organic solvents in many aspects, such as the high dispersibility of silica spheres and their non-volatility. PMID:25985926

Hot-press diffusion welding parameters were developed for a directionally solidified, gamma/gamma prime-delta eutectic alloy. Based on metallography, a good diffusion weld was achieved at 1100 C under 34.5 MPa (5 ksi) pressure for 1 hour. In addition, a dissimilar metal weld between gamma/gamma prime-delta and IN-100 was successfully made at 1100 C under 20.7 MPa (3 ksi) pressure for 1 hour.

In an attempt to explain the influence of space processing on the microstructure of MnBi-Bi, eutectic mixtures were directionally solidified with a sudden change of translation rate. The MnBi fiber spacing was able to adapt to the changing freezing rate as predicted by heat transfer computations. Thus the microstructure adapts more rapidly than the freezing rate could be changed in the present experiments.

Starting from a powder mixture of ketones/urea, gentle heating results in liquefaction below the melting point of the respective components. The back-cover image shows a polarized optical microscopy image of a liquid-crystalline eutectic mixture in the supercooled liquidus, as discussed on page 1287 by N. Fechler and co-workers. This indicates the coupling of the monomers toward larger, preorganized assemblies. From this precursor system, "C2N" carbon is synthesized. PMID:26849666

The electrode potentials of uranium in the melt of the eutectic mixture of lithium, potassium, and cesium chlorides are measured in the temperature range 573-1073 K. Formal standard potentials E U * (III)/U and the main thermodynamic characteristics of uranium trichloride in the LiCl-KCl-CsCl melt are calculated, and the electronic absorption spectra of UCl 6 3- ions are measured.

Developing green solvents with low toxicity and cost is an important issue for the biochemical industry. Synthetic ionic liquids and deep eutectic solvents have received considerable attention due to their negligible volatility at room temperature, high solubilization ability, and tunable selectivity. However, the potential toxicity of the synthetic ionic liquids and the solid state at room temperature of most deep eutectic solvents hamper their application as extraction solvents. In this study, a wide range of recently discovered natural ionic liquids and deep eutectic solvents (NADES) composed of natural compounds were investigated for the extraction of phenolic compounds of diverse polarity. Safflower was selected as a case study because its aromatic pigments cover a wide range of polarities. Many advantageous features of NADES (such as their sustainability, biodegradability combined with acceptable pharmaceutical toxicity profiles, and their high solubilization power of both polar and nonpolar compounds) suggest their potential as green solvents for extraction. Experiments with different NADES and multivariate data analysis demonstrated that the extractability of both polar and less polar metabolites was greater with NADES than conventional solvents. The water content in NADES proved to have the biggest effect on the yield of phenolic compounds. Most major phenolic compounds were recovered from NADES with a yield between 75% and 97%. This study reveals the potential of NADES for applications involving the extraction of bioactive compounds from natural sources. PMID:23710664

Directional solidification experiments were used to measure the transition velocities between the type A and coral eutectic structures in high-purity cast irons and between the type A and type D eutectic structures in S and Te doped cast irons. Introduction of O into the gas atmosphere was found to have little effect on the A {R_arrow} D transition velocities in S doped alloys, but it produced a strong reduction in the A {R_arrow} coral transition velocities in high-purity irons. Transmission electron microscopy revealed interesting variations in the defect structures of the graphite in the flake irons vs the type of flake (A or D) and the type of doping element. Scanning Auger microscopy demonstrated that both S and Te segregate to the iron/graphite interface. In the S doped alloys, type A flakes are generally covered with a monolayer of S with patches of O in the form of iron oxide having a thickness on the order of 2 nm. A series of experiments, including examination of fracture surfaces at the quenched solid/liquid growth front, have shown that S segregates to the iron/graphite interfaces from the liquid at the growth front, but O forms at these interfaces during the cooldown. These results are discussed in relation to current models of eutectic growth in cast irons.

The phase diagram of an organic analog of a metal-metal system involving succinonitrile (SCN) and carbontetrabromide (CTB) shows the formation of a eutectic (0.996 mole fraction of SCN) and a monotectic (0.040 mole fraction of SCN) with a wide range of miscibility gap in the system. The consolute temperature is 111.5°C above the monotectic horizontal. The growth data, determined by measuring the rate of movement of solid-liquid interface in a capillary, at different undercooling (Δ T) suggest that they obey the parabolic law, v= u(Δ T) n, where v is the linear velocity of crystallization and u and n are constants depending on the nature of materials involved. Using enthalpy of fusion of the pure components, the eutectic and the monotectic, entropy of fusion, Jackson's roughness parameter, interfacial energy, size of the critical nucleus and excess thermodynamic functions were calculated. While microstructural investigations of pure components give dendritic microstructures, those of eutectic and monotectic give characteristic lamellar structures.

Continuous and discontinuous NaF fibers, embedded in a NaCl matrix, were produced in space and on earth. The production of continuous fibers in a eutectic mixture is attributed to the absence of convection current in the liquid during solidification in space. Image transmission and optical transmittance measurements of transverse sections of the space-grown and earth-grown ingots were made with a light microscope and a spectrometer. It is shown that better optical properties were obtained from samples grown in space. This was attributed to a better alignment of NaF fibers along the ingot axis. A new concept is advanced to explain the phenomenon of transmittance versus far infrared wavelength of the directionally solidified NaCl-NaF eutectic in terms of the two-dimensional Bragg Scattering and the polarization effect of Rayleigh scattering. This concept can be applied to other eutectic systems as long as the index of refraction of the matrix over a range of wavelengths is known. Experimental data are in agreement with the theoretical prediction.

The stability of hen's egg white lysozyme in different choline chloride-based pseudo-concentrated and neat deep eutectic solvents (DESs) has been studied by means of intrinsic fluorescence and CD spectroscopy. Thermal unfolding experiments carried out in non-diluted urea:choline chloride and glycerol:choline chloride eutectic solvents (UCCl-DES and GCCl-DES, respectively) showed the accumulation at certain temperatures of discrete, partially folded intermediates that displayed a high content of secondary structure and a disrupted tertiary structure. Reversibility of the unfolding process was incomplete in these circumstances, with the urea-based DES showing higher protein structure destabilization upon thermal treatment. On the other hand, aqueous dilution of the eutectic mixtures allowed the recovery of a reversible, two-state denaturation process. Lysozyme activity was also affected in neat and pseudo-concentrated GCCl-DES, with an increasing recovery of activity upon aqueous dilution, and full restoration after DES removal through extensive dialysis. These results suggest that protein interactions at room temperature are reversible and depend on the DES components and on the aqueous content of the original DES dilution. PMID:23722327

The enzymatic preparation of biodiesel has been hampered by the lack of suitable solvents with desirable properties such as high lipase compatibility, low cost, low viscosity, high biodegradability, and ease of product separation. Recent interest in using ionic liquids (ILs) as advanced reaction media has led to fast reaction rates and high yields in the enzymatic synthesis of biodiesel. However, conventional (i.e., cation–anion paired) ILs based on imidazolium and other quaternary ammonium salts remain too expensive for wide application at industrial scales. In this study, we report on newly-synthesized eutectic ILs derived from choline acetate or choline chloride coupled with biocompatible hydrogen-bond donors, such as glycerol. These eutectic solvents have favorable properties including low viscosity, high biodegradability, and excellent compatibility with Novozym® 435, a commercial immobilized Candida antarctica lipase B. Furthermore, in a model biodiesel synthesis system, we demonstrate high reaction rates for the enzymatic transesterification of Miglyol® oil 812 with methanol, catalyzed by Novozym® 435 in choline acetate/glycerol (1 : 1.5 molar ratio). The high conversion (97%) of the triglyceride obtained within 3 h, under optimal conditions, suggests that these novel eutectic solvents warrant further exploration as potential media in the enzymatic production of biodiesel. PMID:21283901

It is well known that irregular eutectics such as Al-Si and Fe-C exhibit larger lamellar spacings and undercoolings compared to the predictions made by the Jackson and Hunt (JH) theory. In this paper, we reexamine the JH theory and relax some of the assumptions used in that treatment. The modified theoretical model has enhanced capabilities to predict the lamellar spacing in both regular and irregular eutectics. For the Al-Si system in particular we identified two different spacing selection mechanisms:a) for a particular growth rate, a nearly isothermal interface can be achieved at a unique minimum spacing lambda(sub I); b) the average spacing in the microstructure (lambda(sub av) greater than lambda(sub I)) is essentially dictated by the undercooling of the faceted phase. Based on the modified theoretical model a semi-empirical expression has been developed to account for the influence of the temperature gradient. Application of a Mullin and Sekerka type stability analysis for eutectics will also be presented and the results compared to the modified JH model. It will be shown that the both theoretical approaches are in good agreement with each other and also with the published experimental measurements.

The role of gravity on Bridgman-Stockharger directional solidification of eutectic Bi/MnBi has been studied in reduced gravity aboard NASA sounding rocket SPAR flight experiments and contrasted with normal gravity investigations. The directional solidification of eutectic Bi/MnBi results in a low volume fraction, faceted/nonfaceted aligned rod eutectic whose MnBi rod size, interrod spacing, thermal and magnetic properties are sensitive functions of solidification processing conditions. The morphology of the low-gravity samples showed striking differences compared with identically processed, normal gravity samples grown in the same apparatus. The MnBi rod diameter and interrod spacing distributions were significantly smaller, approximately 50 percent, for the low gravity samples compared with identically processed one gravity samples. Accompanying the smaller MnBi rod diameters observed in the flight samples, was an increase in permanent magnet properties which reached greater than 97 percent of the theoretical maximum. Gravitationally induced thermal instabilities in one-gravity which result in irregular interface movement and associated difficulty of the faceted MnBi phase to branch are suggested to explain the morphological differences between one and low gravity solidification.

In this paper, we reexamine the Jackson and Hunt (JH) theory and relax the assumption of isothermal solid/liquid interface(SLI) used in their treatment. A modification of the term B. in the expression of the solute concentration profile is also proposed. Based on the predictions of this modified theory the traditional definitions of regular and irregular eutectics are discussed. For regular eutectics the new model identifies a range of spacing within the limits defined by the minimum undercooling of the alpha and beta phase. For the irregular Al-Si eutectic system in particular we identified two different spacing selection mechanisnis: a) for a particular growth rate, a nearly isothermal interface can be achieved at a unique minimum spacing lambda(sub I); b) the average spacing in the microstructure (lambda(sub av) > lambda(sub I)) is essentially dictated by the undercooling of the faceted phase. Based on the modified theoretical model a semi-empirical expression has been developed to account for the influence of the temperature gradient. The theoretical calculations have been found to be in good agreement with the published experimental measurements.

The aim of present study were to arrest the problem of content uniformity without the use of harmful organic solvent and to improve ex vivo permeability of captopril, a low dose class III drug as per biological classification system. Eutectic mixture of camphor and menthol was innovatively used in the work. Captopril solution in eutectic mixture was blended with Avicel PH 102 and then the mixture was blended with mannitol in different ratios. Formulated batches were characterized for angle of repose and Carr's index. A selected batch was filled in hard gelatin capsule. Tablet dosage form was also developed. Capsules and tablets were characterized for in vitro drug release in 0.1N HCl. Additionally, the captopril tablets were analyzed for content uniformity and ex vivo drug permeation study using rat ileum in modified apparatus. The measurement of angle of repose and Carr's index revealed that the powder blend exhibited good flow property and compressibility. The captopril capsules and tablets exhibited immediate drug release in 0.1 N HCl. The captopril tablets passed content uniformity test as per IP 1996. Ex vivo permeation of captopril, formulated with eutectic mixture, was faster than control. The permeation was increased by 15% at the end of 3 h. Tablets and capsule exhibited reasonable short term stability with no considerable change in performance characteristics. PMID:20376214

The effects of directional solidification processing on the microstructural, compositional, and magnetic properties of near eutectic Co-Sm alloys (about 9 at. pct Sm) have been studied. Initial investigations have been performed at modest thermal gradients in the liquid, G(L) less than 60 C/cm and over a range of furnace (solidification) velocities, V = 0.8 45.4 cm/h. The primary dendrite spacing for near eutectic Sm2Co17/Co scaled with 1/sq rt V and varied from about 50 microns for V greater than or equal to 20 cm/h to hundreds of microns for V less than 10 cm/h, while the rod eutectic diameter and interrod spacing were an order of magnitude smaller. For both dendritic and cooperative growth, the associated permanent magnet properties were rather poor, e.g., remanence less than 4 kG and coercive force less than 1 kOe for the smallest dendrite and rod diameter dimensions encountered, although the magnetic hardness for the rod eutetic was larger than for the dendritic microstructure. Magnetization as a function of sample orientation indicated that the easy axis of magnetization was primarily along the direction of solidification for both ferromagnetic phases.

The aim of present study were to arrest the problem of content uniformity without the use of harmful organic solvent and to improve ex vivo permeability of captopril, a low dose class III drug as per biological classification system. Eutectic mixture of camphor and menthol was innovatively used in the work. Captopril solution in eutectic mixture was blended with Avicel PH 102 and then the mixture was blended with mannitol in different ratios. Formulated batches were characterized for angle of repose and Carr's index. A selected batch was filled in hard gelatin capsule. Tablet dosage form was also developed. Capsules and tablets were characterized for in vitro drug release in 0.1N HCl. Additionally, the captopril tablets were analyzed for content uniformity and ex vivo drug permeation study using rat ileum in modified apparatus. The measurement of angle of repose and Carr's index revealed that the powder blend exhibited good flow property and compressibility. The captopril capsules and tablets exhibited immediate drug release in 0.1 N HCl. The captopril tablets passed content uniformity test as per IP 1996. Ex vivo permeation of captopril, formulated with eutectic mixture, was faster than control. The permeation was increased by 15% at the end of 3 h. Tablets and capsule exhibited reasonable short term stability with no considerable change in performance characteristics. PMID:20376214

The chemical oxidation states of NpO2+, Np4+ and Np3+ in NaCl-CsCl eutectic were controlled by using Cl2, O2, H2 and Ar gas mixtures, the redox behavior and electronic absorption properties of their Np ions were studied. The Np4+ was prepared from NpO2Cl by bubbling Cl2 gas into the melt in the presence of carbon rod. Np3+ was quantitatively prepared by bubbling H2-Ar gas mixture. The molar absorptivities of NpO2+, Np4+ and Np3+ were determined in molten NaCl-CsCl eutectic at 923 K and hypersensitive transitions of Np4+ and Np3+ ions were assigned. Since the polarizing ability of the cations in the NaCl-CsCl eutectic is lower than that in some other melts, it has been shown that the coordination symmetry of the Np-Cl complex is higher. In the electrochemical measurement of Np4+, the cathodic current for the reduction of Np4+ was found to be controlled by the diffusion of Np4+. The temperature dependence of the diffusion coefficient between 823 and 923 K was formulated to be lnD=-4304/T-6.172. The formal redox potential of the Np4+|Np3+ couple depended on the temperature, this dependence was formulated as ENp|Np∘'=-1.313+6.210×10-4T V (vs. Cl2|Cl-).

TNAZ is a high performing explosive that is melt castable. However, the casting process can be problematic since TNAZ has a high vapor pressure exacerbated by a fairly high melting temperature. In order to mitigate the ill effects of its high vapor pressure, including a lower melting explosive was explored by making a series of mixtures of TNAZ and R-Salt. Initially, a eutectic temperature and composition was theoretically determined. Then a phase diagram was constructed from a series and mixtures by differential scanning calorimetery (DSC). The vapor pressure of the eutectic composition was determined by thermogravimetric analysis (TGA). Cylinder testing of the eutectic composition was carried out in copper tubes, 5'' long with 1/2 ``inner diameter and 1/16'' thick walls. The detonation velocity was measured using wire switches along the cylinder length and the expanding wall velocity was measured using PDV gauges. A rough evaluation of JWL equation-of-state parameters has been carried out. A more detailed evaluation is in progress.

Cellular eutectic microstructures with fully lamellar morphology were observed in the directionally solidified Ni-31Al-32Cr-6Mo (at%) hypereutectic alloy at withdrawal rates of 15, 25 and 50 μm/s, but the morphologies of cellular microstructures did not change consecutively with increasing withdrawal rate. The growth interfaces were deep cellular at withdrawal rates of 15 and 50 μm/s, but it changed to be shallow cellular at rate of 25 μm/s. The reason is that the interface undercooling comes to minimum at the middle rate of 25 μm/s. If the interface undercooling decreases, the tendency of constitutional undercooling will be weaken. The small constitutional undercooling will increase the interface stability, so that the interface morphology changes from deep cellular to shallow cellular. The shallow cellular growth interface led to a perfect cellular eutectic microstructure, which was analogous to the planar eutectic microstructure. In this case, the widths of the intercellular regions were narrowest, no coarse or irregular plates existed at the cell boundaries, and the thicknesses of the lamellae were almost uniform. The properties of the alloy may be markedly improved.

The incorporation of ionic liquid (IL) chemistry into functional polymers has extended the properties and applications of polyelectrolytes. However, ILs are expensive due to the presence of fluorinated anions or complicated synthetic steps which limit their technological viability. Here, we show a new family of poly(ionic liquid)s (PILs) which are based in cheap and renewable chemicals and involves facile synthetic approaches. Thus, deep eutectic monomers (DEMs) are prepared for the first time by using quaternary ammonium compounds and various hydrogen bond donors such as citric acid, terephthalic acid or an amidoxime. The deep eutectic formation is made through a simple mixing of the ingredients. Differential scanning calorimetry, nuclear magnetic resonance (NMR) and computational studies reveal the formation of the DEMs due to the ionic interactions. The resulting DEMs are liquid which facilitates their polymerization using mild photopolymerization or polycondensation strategies. Spectroscopic characterizations reveal the successful formation of the polymers. By this way, a new family of PILs can be synthesized which can be used for different applications. As an example, the polymers show promising performance as solid CO2 sorbents. Altogether the deep eutectic monomer route can lead to non-toxic, cheap and easy-to-prepare alternatives to current PILs for different applications. PMID:26954303

A straightforward and reliable method to determine densities of molten salts at high temperatures was de-veloped by Janz and Lorenz several years ago.[1] This method was followed in order to determine the density of the LiF/Li2S eutectic[2] over the temperature range of 1176 to 1355 K in which the eutectic is liquid. The rel-ative lack of data for this eutectic is surprising given its potential usefulness in the study of advanced batteries'31 and electrowinning of metals from molten sulfides.[41] The method is based on the fact that a solid piece of metal of known volume suspended from a pan balance into a molten salt will weigh less than if it were sus-pended in air at the same temperature. This difference in weight measured in grams will be equal to the buoyant force of the liquid at that temperature. The density of the salt bath can then readily be determined by dividing this difference by the volume of the solid piece of metal that is immersed in the bath. The procedure can be re-peated to give density values over a range of temperatures.

We present the first microlensing candidate for a free-floating exoplanet-exomoon system, MOA-2011-BLG-262, with a primary lens mass of M {sub host} ∼ 4 Jupiter masses hosting a sub-Earth mass moon. The argument for an exomoon hinges on the system being relatively close to the Sun. The data constrain the product M{sub L} π{sub rel} where M{sub L} is the lens system mass and π{sub rel} is the lens-source relative parallax. If the lens system is nearby (large π{sub rel}), then M{sub L} is small (a few Jupiter masses) and the companion is a sub-Earth-mass exomoon. The best-fit solution has a large lens-source relative proper motion, μ{sub rel} = 19.6 ± 1.6 mas yr{sup –1}, which would rule out a distant lens system unless the source star has an unusually high proper motion. However, data from the OGLE collaboration nearly rule out a high source proper motion, so the exoplanet+exomoon model is the favored interpretation for the best fit model. However, there is an alternate solution that has a lower proper motion and fits the data almost as well. This solution is compatible with a distant (so stellar) host. A Bayesian analysis does not favor the exoplanet+exomoon interpretation, so Occam's razor favors a lens system in the bulge with host and companion masses of M{sub host}=0.12{sub −0.06}{sup +0.19} M{sub ⊙} and m{sub comp}=18{sub −10}{sup +28} M{sub ⊕}, at a projected separation of a{sub ⊥}=0.84{sub −0.14}{sup +0.25} AU. The existence of this degeneracy is an unlucky accident, so current microlensing experiments are in principle sensitive to exomoons. In some circumstances, it will be possible to definitively establish the mass of such lens systems through the microlensing parallax effect. Future experiments will be sensitive to less extreme exomoons.

The separation characteristics of surrogate rare-earth fission products in a eutectic (LiCl-KCl) molten salt were investigated. This system is based on the eutectic salt used for the pyroprocessing treatment of used nuclear fuel (UNF). The investigation was performed using an integrated rare-earth separation apparatus comprising a precipitation reactor, a solid detachment device, and a layer separation device. To separate rare-earth fission products, a phosphate precipitation method using both Li3PO4 and K3PO4 as a precipitant was performed. The use of an equivalent phosphate precipitant composed of 0.408 molar ratio-K3PO4 and 0.592 molar ratio-Li3PO4 can preserve the original eutectic ratio, LiCl-0.592 molar ratio (or 45.2 wt%), as well as provide a high separation efficiency of over 99.5% under conditions of 550 °C and Ar sparging when using La, Nd, Ce, and Pr chlorides. The mixture of La, Nd, Ce, and Pr phosphate had a typical monoclinic (or monazite) structure, which has been proposed as a reliable host matrix for the permanent disposal of a high-level waste form. To maximize the reusability of purified eutectic waste salt after rare-earth separation, the successive rare-earth separation process, which uses both phosphate precipitation and an oxygen sparging method, were introduced and tested with eight rare-earth (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) chlorides. In the successive rare-earth separation process, the phosphate reaction was terminated within 1 h at 550 °C, and a 4-8 h oxygen sparging time were required to obtain over a 99% separation efficiency at 700-750 °C. The mixture of rare-earth precipitates separated by the successive rare-earth separation process was found to be phosphate, oxychloride, and oxide. Through the successive rare-earth separation process, the eutectic ratio of purified salt maintained its original value, and impurity content including the residual precipitant of purified salt can be minimized.

Deep eutectic solvent (DES) is a room temperature liquid typically formed by mixing two solid compounds, such as a quaternary ammonium salt (QAS) (e.g. choline chloride) and a hydrogen bond donor (HBD) (e.g. urea or a carboxylic acid) at their eutectic composition. Very often, a range of room temperature liquids can also be obtained near the eutectic composition. Hence, it is more convenient to introduce a more general term deep eutectic solvent derivatives (DESDs) to describe a wide range of DES-like derivatives including those derived from ternary mixtures. The melting point of the mixture is lowered because the hydrogen bonding between DESD components reduces the lattice energy of components of the eutectic system. Based on the analysis of available data for 22 such choline chloride-based DES pairs, we found that the observed melting point depression can be statistically correlated with the difference between the hydrogen bonding contribution (δh) and the polar contribution (δp) to the solubility parameter of the hydrogen bond donor (HBD) component. The correlation was validated with a new DESD based on glycolic acid and choline chloride, which form DESDs at a molar ratio between 1:1 and 1:4 with DES-like properties. As a room temperature liquid, this DESD exhibits a wide range of solubility enhancement on several weakly basic poorly water-soluble drugs. For example, the solubility of itraconazole, piroxicam, lidocaine, and posaconazole has been observed to increase by 6700, 430, 28, and 6400-fold, respectively as compared to their aqueous solubility at room temperature. Furthermore, another new ternary DESD based on choline chloride, glycolic acid, and oxalic acid at a molar ratio of 1:1.6:0.4 is shown to further increase the solubility of itraconazole to a remarkable level of 5.36mg/mL (a 53,600-fold increase!). Because the components of such DESDs can include those biodegradable ones that had previously been used in formulated human products, the potential

The Fe-FeS system maintains a eutectic temperature of 990 ± 10 °C to at least 8 GPa if starting materials and pressure media are rigorously dehydrated. Literature reports of pressure-induced freezing point depression of the eutectic for the Fe-FeS system are not confirmed. Modest addition of oxygen alone is confirmed to cause negligible freezing point depression at 6 GPa. Addition of H alone causes a progressive decrease in the eutectic temperature with P in the Fe-FeS-H system to below 965 °C at 6 GPa to below 950 °C at 8 GPa. It is our hypothesis that moisture contamination in unrigorously dried experiments may be an H source for freezing point depression. O released from H2O disproportionation reacts with Fe and is sequestered as ferropericlase along the sample capsules walls, leaving the H to escape the system and/or enter the Fe-FeS mixture. The observed occurrence of ferropericlase on undried MgO capsule margins is otherwise difficult to explain, because an alternate source for the oxygen in the ferropericlase layer is difficult to identify. This study questions the use of pressure-depressed Fe-S eutectic temperatures and suggests that the lower eutectic temperatures sometimes reported are achieved by moving into the ternary Fe-S-H system. These results adjust slightly the constraints on eutectic temperatures allowed for partly solidified cores on small planets. H substantially diminishes the temperature extent of the melting interval in Fe-S by reducing the melting points of the crystalline phases more than it depresses the eutectic.

The mechanical behavior and microstructure of eutectic Bi-Sn and In-Sn solders were studied in parallel in order to better understand high temperature deformation of these alloys. Bi-Sn solder joints were made with Cu substrates, and In-Sn joints were made with either Cu or Ni substrates. The as-cast microstructure of Bi-Sn is complex regular, with the two eutectic phases interconnected in complicated patterns. The as-cast microstructure of In-Sn depends on the substrate. In-Sn on Cu has a non-uniform microstructure caused by diffusion of Cu into the solder during sample preparation, with regions of the Sn-rich {gamma} phase imbedded in a matrix of the In-rich {beta} phase. The microstructure of In-Sn on Ni is uniform and lamellar and the two phases are strongly coupled. The solders deform non-uniformly, with deformation concentrating in a band along the length of the sample for Bi-Sn and In-Sn on Cu, though the deformation is more diffuse in In-Sn than in Bi-Sn. Deformation of In-Sn on Ni spreads throughout the width of the joint. The different deformation patterns affect the shape of the stress-strain curves. Stress-strain curves for Bi-Sn and In-Sn on Cu exhibit sharp decays in the engineering stress after reaching a peak. Most of this stress decay is removed for In-Sn on Ni. The creep behavior of In-Sn also depends on the substrate, with the creep deformation controlled by the soft P phase of the eutectic for In-Sn on Cu and controlled by the harder {gamma} phase for In-Sn on Ni. When In-Sn on Ni samples are aged, the microstructure coarsens and changes to an array of {gamma} phase regions in a matrix of the {beta} phase, and the creep behavior changes to resemble that of In-Sn on Cu. The creep behavior of Bi-Sn changes with temperature. Two independent mechanisms operate at lower temperatures, but there is still some question as to whether one or both of these, or a third mechanism, operates at higher temperatures.

This paper attempts to gain an understanding of the effect of lamellar length scale on the mechanical properties of two-phase metal-intermetallic eutectic structure. We first develop a molecular dynamics model for the in-situ grown eutectic interface followed by a model of deformation of Al-Al{sub 2}Cu lamellar eutectic. Leveraging the insights obtained from the simulation on the behaviour of dislocations at different length scales of the eutectic, we present and explain the experimental results on Al-Al{sub 2}Cu eutectic with various different lamellar spacing. The physics behind the mechanism is further quantified with help of atomic level energy model for different length scale as well as different strain. An atomic level energy partitioning of the lamellae and the interface regions reveals that the energy of the lamellae core are accumulated more due to dislocations irrespective of the length-scale. Whereas the energy of the interface is accumulated more due to dislocations when the length-scale is smaller, but the trend is reversed when the length-scale is large beyond a critical size of about 80 nm.

Directionally solidified (DS) intermetallic and ceramic-based eutectic alloys with an in-situ composite microstructure containing finely distributed, long aspect ratio, fiber, or plate reinforcements are being seriously examined for several advanced aero-propulsion applications. In designing these alloys, additional solutes need to be added to the base eutectic composition in order to improve heir high-temperature strength, and provide for adequate toughness and resistance to environmental degradation. Solute addition, however, promotes instability at the planar liquid-solid interface resulting in the formation of two-phase eutectic "colonies." Because morphology of eutectic colonies is very similar to the single-phase cells and dendrites, the stability analysis of Mullins and Sekerka has been extended to describe their formation. Onset of their formation shows a good agreement with this approach; however, unlike the single-phase cells and dendrites, there is limited examination of their growth speed dependence of spacing, morphology, and spatial distribution. The purpose of this study is to compare the growth speed dependence of the morphology, spacing, and spatial distribution of eutectic cells and dendrites with that for the single-phase cells and dendrites.

The vapor-liquid-solid mechanism of nanowire (NW) growth requires the presence of a liquid at one end of the wire; however, Au-catalyzed Ge nanowire growth by chemical vapor deposition can occur at approximately 100 degrees C below the bulk Au-Ge eutectic. In this paper, we investigate deep sub-eutectic stability of liquid Au-Ge catalysts on Ge NWs quantitatively, both theoretically and experimentally. We construct a binary Au-Ge phase diagram that is valid at the nanoscale and show that equilibrium arguments, based on capillarity, are inconsistent with stabilization of Au-Ge liquid at deep sub-eutectic temperatures, similar to those used in Ge NW growth. Hot-stage electron microscopy and X-ray diffraction are used to test the predictions of nanoscale phase equilibria. In addition to Ge supersaturation of the Au-Ge liquid droplet, which has recently been invoked as an explanation for deep sub-eutectic Ge NW growth, we find evidence of a substantial kinetic barrier to Au solidification during cooling below the nanoscale Au-Ge eutectic temperature. PMID:19206662

The influence of segregation due to thermal convection on the microstructure of Sn-Cu{sub 6}Sn{sub 5} fibrous eutectic alloys is studied in a Bridgman type configuration. The eutectic microstructure is characterized by means of image analysis, X-ray diffraction and scanning and transmission electron microscopy. In the absence of segregation, the eutectic is regular and its growth controlled by that of the Cu{sub 6}Sn{sub 5} fibers. The effect of interphases on eutectic spacing, through orientation relationships between fibers and matrix, is also evidenced. The influence of segregation can be summed up by the following effects. At first, in agreement with the Jackson and Hunt model, it leads to a variation of the eutectic spacing which results from a variation of the fiber volume fraction. Then, the spacing is much greater than the one obtained in the absence of segregation, due to a different tin growth plane and non-optimized fiber/matrix orientation relationships. Finally, the absence of steady state leads to a large dispersion of the spacing associated with a microstructural disorder.

Deep eutectic solvents (DESs) are exemplars of systems with the ability to form neutral, ionic and doubly ionic H-bonds. Herein, the pairwise interactions of the constituent components of the choline chloride-urea DES are examined. Evidence is found for a tripodal CHCl doubly ionic H-bond motif. Moreover it is found that the covalency of doubly ionic H-bonds can be greater than, or comparable with, neutral and ionic examples. In contrast to many traditional solvents, an "alphabet soup" of many different types of H-bond (OHO[double bond, length as m-dash]C, NHO[double bond, length as m-dash]C, OHCl, NHCl, OHNH, CHCl, CHO[double bond, length as m-dash]C, NHOH and NHNH) can form. These H-bonds exhibit substantial flexibility in terms of number and strength. It is anticipated that H-bonding will have a significant impact on the entropy of the system and thus could play an important role in the formation of the eutectic. The 2 : 1 urea : choline-chloride eutectic point of this DES is often associated with the formation of a [Cl(urea)2](-) complexed anion. However, urea is found to form a H-bonded urea[choline](+) complexed cation that is energetically competitive with [Cl(urea)2](-). The negative charge on [Cl(urea)2](-) is found to remain localised on the chloride, moreover, the urea[choline](+) complexed cation forms the strongest H-bond studied here. Thus, there is potential to consider a urea[choline](+)·urea[Cl](-) interaction. PMID:27328990

Manganese, which may be used in ductile cast iron as a potent hardenability promoter, segregates in the intercellular region. This segregation becomes more severe as a consequence of poor inoculation, low cooling rate, or increasing of nominal Mn content in the alloy. In severely Mn-segregated regions, Mn eutectic carbide may be formed, which has a deteriorating effect on the mechanical properties of casting. In this study, a 1 Pct Mn ductile iron was used to investigate the chemical composition and crystal structure of the Mn eutectic carbide by electron microscopy (scanning and transmission), X-ray, and an electron probe microanalyzer (EPMA). Transmission electron microscope (TEM) and X-ray studies show that the crystal structure of carbide is orthorhombic with lattice parameters of a = 14.825, b = 11.415, and c = 8.880 (Å). The concentrations of Mn, Si, and Cr in carbide, analyzed by scanning electron microscope-energy-dispersive X-ray spectrometer (SEM-EDX) and transmission electron microscope-energy-dispersive X-ray spectrometer (TEM-EDX), were 5.0 to 7.0, 0.5 to 2.8 and 1.5 to 2.2 (wt Pct), respectively. The ratio of Fe plus other metal atoms to C was calculated from EPMA experiments to be 2.5-2.9. It was shown that by diminishing Mn segregation, precipitated eutectic carbide can be reduced. It is expected that this can be achieved by reducing nominal content of Mn or by increasing nodule count.

In this paper we report on two related topics: Kinetic Monte Carlo simulations of the steady state growth of rod eutectics from the melt, and a study of the surface roughness of binary alloys. We have implemented a three dimensional kinetic Monte Carlo (kMC) simulation with diffusion by pair exchange only in the liquid phase. Entropies of fusion are first chosen to fit the surface roughness of the pure materials, and the bond energies are derived from the equilibrium phase diagram, by treating the solid and liquid as regular and ideal solutions respectively. A simple cubic lattice oriented in the {100} direction is used. Growth of the rods is initiated from columns of pure B material embedded in an A matrix, arranged in a close packed array with semi-periodic boundary conditions. The simulation cells typically have dimensions of 50 by 87 by 200 unit cells. Steady state growth is compliant with the Jackson-Hunt model. In the kMC simulations, using the spin-one Ising model, growth of each phase is faceted or nonfaceted phases depending on the entropy of fusion. There have been many studies of the surface roughening transition in single component systems, but none for binary alloy systems. The location of the surface roughening transition for the phases of a eutectic alloy determines whether the eutectic morphology will be regular or irregular. We have conducted a study of surface roughness on the spin-one Ising Model with diffusion using kMC. The surface roughness was found to scale with the melting temperature of the alloy as given by the liquidus line on the equilibrium phase diagram. The density of missing lateral bonds at the surface was used as a measure of surface roughness.

The surface structure of the liquid phase of the Au{sub 72}Ge{sub 28} eutectic alloy has been measured using resonant and nonresonant x-ray reflectivity and grazing incidence x-ray diffraction. In spite of the significant differences in the surface tension of liquid Ge and Au the Gibbs adsorption enhancement of Ge concentration at the surface is minimal. This is in striking contrast to all the other binary alloys with large differences in the respective surface tensions measured up to date. In addition there is no evidence of the anomalous strong surface layering or in-plane crystalline order that has been reported for the otherwise quite similar liquid Au{sub 82}Si{sub 18} eutectic. Instead, the surface of eutectic Au{sub 72}Ge{sub 28} is liquidlike and the layering can be explained by the distorted crystal model with only slight modifications to the first layer.

Containerless processing and rapid solidification techniques were used to process Nb-Si alloys in the Nb-rich eutectic range. Electromagnetically levitated drops were melted and subsequently splat-quenched from different temperatures. A variety of eutectic morphologies was obtained as a function of the degree of superheating or undercooling of the drops prior to splatting. Metallic glass was observed only in drops quenched from above the melting temperature. Microstructures of splats deeply undercooled prior to quenching were very fine and uniform. These results are discussed in terms of classic nucleation theory concepts and the expected heat evolution at different regions of the splat during the rapid quenching process. The locations of the coupled-zone boundaries for the alpha-Nb + Nb3Si eutectic are also suggested.

An improved method for preparing a cermet comprises preparing a compact having about 85 to 95 percent theoretical density from a mixture of metal and metal oxide powders from a system containing a eutectic composition, and inductively heating the compact in a radiofrequency field to cause the formation of an internal molten zone. The metal oxide particles in the powder mixture are effectively sized relative to the metal particles to permit direct inductive heating of the compact by radiofrequency from room temperature. Surface melting is prevented by external cooling or by effectively sizing the particles in the powder mixture.

Density of low-temperature eutectic in magnesium-lead system (83.06 at. % Pb) has been measured by gamma-raying of the samples with narrow beam from cesium-137 isotope over the temperature range 293-1000 K of solid and liquid states. Approximation density dependences have been obtained and data of this work and other authors have been compared. Reference tables of temperature dependences of the alloy thermal properties have been compiled for the entire range of measurements and their errors estimated. It is shown that differences in the values of volumetric changes obtained during melting and crystallization are bound with the metastable β'-phase formation.

A space shuttle experiment employing the General Purpose Furnace in its isothermal mode of operation is currently manifested for flight circa 1989. The aim of this experiment was to investigate the role of gravity in a slowly, and isothermally, cooled sample of a binary Pb - 15 wt percent Sn alloy. Ground based work in support of the microgravity experiment is discussed. In particular, it is shown that fraction eutectic measurements using an image analyzer, can be used to satisfactorily describe macrosegregation occurring in these slowly cooled ingots.

In this study, we demonstrated a new class of frequency-switchable metamaterial absorber in the X-band. Eutectic gallium-indium (EGaIn), a liquid metal alloy, was injected in a microfluidic channel engraved on polymethyl methacrylate (PMMA) to achieve frequency switching. Numerical simulation and experimental results are presented for two cases: when the microfluidic channels are empty, and when they are filled with liquid metal. To evaluate the performance of the fabricated absorber prototype, it is tested with a rectangular waveguide. The resonant frequency was successfully switched from 10.96 GHz to 10.61 GHz after injecting liquid metal while maintaining absorptivity higher than 98%. PMID:26561815

We report two cases of newborns who developed marked local edema after application of a eutectic mixture of local anesthetic (EMLA) topical anesthetic cream for neonatal male circumcision (NMC). Although local edema and erythema are known potential side effects of EMLA cream, a common anesthetic used for NMC, the loss of landmarks precluding safe NMC has not previously been reported, and is described here. Although we cannot recommend an alternate local anesthetic for neonates with this reaction to EMLA, based on a review of the published data we think that serious systemic adverse events related to EMLA are extremely rare. PMID:23102766

During rapid solidification substantial amounts of undercooling are in general required for formation of metastable phases. Crystallization at varying levels of undercooling and melting of metastable phases were studied during slow cooling and heating of emulsified PB-Sn alloys. Besides the experimental demonstration of the reversibility of metastable phase equilibra, two different principal solidification paths have been identified and compared with the established metastable phase diagram and predictions from classical nucleation theory. The results suggest that the most probable solidification path is described by the 'step rule' resulting in the formation of metastable phases at low undercooling, whereas the stable eutectic phase mixture crystallizes without metastable phase formation at high undercooling.

An attempt was made to improve on the properties of the candidate jet engine turbine blade material AG-60, a gamma/gamma prime-alpha Mo eutectic composite. Alloy 38 (AG-170) was evaluated in the greatest detail. This alloy, Ni-5.88 A1-29.74 Mo-1.65 V-1.2C Re (weight percent), represents an improvement beyond AG-60, based on mechanical testing of the transverse and/or longitudinal orientations over a range of temperatures in tension, shear, rupture, and rupture after thermal exposure. It is likely that other alloys in the study represent a similar improvement.

The compatibility of AISI 316 L stainless steel with the Li 17Pb 83, eutectic has been studied in the temperature range 623-873 K for times up to 6000 h. In the corrosion layers formed there is a strong Ni depletion and Pb and Li penetration in the matrix. Tests at 623 K in Li 17Pb 83 on notched tensile specimens under a constant uniaxial tensile load, below the engineering yield stress, have evidenced that. many cracks filled with Pb and possibly Li are formed after relatively short times.

The spatial profile of the thermal transients that occur during and following the current pulsing associated with Peltier Interface Demarcation during directional solidification is studied. Results for pure Bi are presented in detail and compared with corresponding results for the Bi/MnBi eutectic. Significant thermal transients occur throughout the sample that can be accounted for by the Peltier effect, the Thomson effect, and Joule heating. These effects are separated and their behavior is studied as a function of time, current density, and position with respect to the solid/liquid interface.

This paper reviews selected parts of the current literature relevant to thermo-mechanical fatigue mechanisms in eutectic tin-lead solder, and suggests a general outline to account for some observed failures. The field is found to be complex. One recent experimental study finds some failure modes to be sensitive to joint geometry. Attempts to extrapolate from test environments to service environments have had only limited success. Much work remains to be done before fatigue failures in this material can be considered as under practical control.

In this study, we demonstrated a new class of frequency-switchable metamaterial absorber in the X-band. Eutectic gallium-indium (EGaIn), a liquid metal alloy, was injected in a microfluidic channel engraved on polymethyl methacrylate (PMMA) to achieve frequency switching. Numerical simulation and experimental results are presented for two cases: when the microfluidic channels are empty, and when they are filled with liquid metal. To evaluate the performance of the fabricated absorber prototype, it is tested with a rectangular waveguide. The resonant frequency was successfully switched from 10.96 GHz to 10.61 GHz after injecting liquid metal while maintaining absorptivity higher than 98%. PMID:26561815

A eutectic alloy, Fe-13.6CR-3.7Al+9TaC, was directionally solidified in a high gradient furnace, producing a microstructure of alined TaC fibers in an oxidation resistant alpha-iron matrix. Tensile and stress rupture properties, thermal cycling resistance, and microstructures were evaluated. The alloy displays at 1000 C an ultimate tensile strength of 58 MPa and a 100-hour rupture life at a stress of 21 MPa. Thermal cycling to 1100 C induces faceting in the TaC fibers.

Severe plastic deformation in an eutectic tin-lead alloy is studied by imposing fast bending at room temperature, in an attempt to examine the microstructural response in the absence of thermally activated diffusion processes. A change in microstructure due to this purely mechanically imposed load is observed: the tin-rich matrix phase appears to be extruded out of the narrow region between neighboring layers of the lead-rich phase and alterations in the colony structure occur. A micromechanism is proposed to rationalize the experimental observations.

The eutectic alloy Ni-20.0%Cb-2.5%Al-6.0%Cr was tested in short-term creep and long-term exposure to service conditions to assess its suitability for high temperature turbine blade applications. Long-time exposure showed the lamellar microstructure of the alloy to be exceptionally stable. Other properties tested were notch sensitivity, isothermal and thermomechanical fatigue strength, shear strength, and transverse ductility. It was shown that this alloy is superior to the best currently available directionally solidified superalloys over the temperature/stress conditions encountered in turbine airfoils.

A lead zirconate titanate(PZT)-Si energy harvester cantilever with PZT bulk ceramics is fabricated by eutectic bonding, polishing and dicing processes. The feasibility of this process is studied using a successful operation of the cantilever in both actuation and harvesting modes. The first prototype made from a PZT-Au-Si cantiliever is tested. The testing results show the voltage output of 632 mV at the frequency of 815 Hz when the excitation acceleration is 0.5 g. The PZT and silicon layers are bonded together to form a sandwiched structure using a gold layer as an intermediate layer.

Continuous and discontinuous lithium fluoride fibers embedded in a sodium chloride matrix were produced in space and on Earth, respectively. The production of continuous fibers in a eutectic mixture was attributed to the absence of convective current in the liquid during solidification in space. Image transmission and optical transmittance measurements of transverse sections of the space-grown and Earth-grown ingots were made with a light microscope and a spectrometer. It was found that better optical properties were obtained from samples grown in space. This was attributed to a better alignment of lithium fluoride fibers along the growth direction.

Electrochemical behaviour of uranium was studied in the low melting ternary LiCl-KCl-CsCl eutectic at 573-1073 K employing potentiometry, cyclic voltammetry and chronopotentiometry. Uranium electrode potentials were measured directly and U(III)/U(IV) red-ox potentials were determined from the results of cyclic voltammetry measurements. Formal standard electrode and red-ox potentials of uranium, and thermodynamic properties of uranium chlorides in the studied melt were calculated. Diffusion coefficients of U(III) and U(IV) ions were determined using cyclic voltammetry and chronopotentiometry.

This study was of the effects moderately low Au concentrations ({le} 10 wt%) have on the mechanical properties and microstructure of an eutectic Sn/Pb alloy. Vibration (60--90 Hz swept sine wave for 30 hours) and thermal cycling (0--110C for 1450 cycles) reliability tests were performed on fine pitch leaded chip carriers using eutectic Sn/Pb solder on PCBs (printed circuit boards) with 0, 5, 10, 20, and 50{mu}in nominal Au thicknesses. Testing was also performed on double shear creep specimens consisting of arrays of regular pitch joints. There was a dramatic increase in the number of joints containing voids with increasing Au concentration, an effect more pronounced in the creep joints than in the reliability joints. These voids tended to coalesce and grow during rework simulation of the reliability joints. AuSn{sub 4} intermetallics present in toe of 4.8 wt% (50 {mu}in) Au vibration joints rotated from initial vertical perpendicular to surface of PCB metallization, solidification positions to roughly horizontal (parallel to plating surface) orientations during rework simulation and during aging of the parts. The AuSn{sub 4} intermetallics in the toe of the 4.8 wt% (50{mu}in) Au reflowed joints also rotated after vibration testing. No joint failures were observed in either vibration tested or thermally cycled specimens. Cracks formed in some of the vibration tested specimen joints under the heel of the gull-wing lead at Pb-rich phases. Thermally cycled specimens showed eutectic microstructure and intermetallic coarsening without crack formation. Creep tests showed loss of the superplasticity in eutectic Sn/Pb alloys with even the lowest Au concentration tested of 0.2 wt% Au. Intermetallic rotation was not a factor in crack propagation, but void presence was. Cracks tended to form in joints containing voids before forming in void-free joints. Crack propagation followed Sn/Sn grain boundaries and Sn/Pb phase boundaries from Pb-rich phase to Pb-rich phase.

In order to assess the susceptibility of candidate structural materials to liquid metal embrittlement, this work investigated the tensile behaviors of ferritic-martensitic steel in static lead bismuth eutectic (LBE). The tensile tests were carried out in static lead bismuth eutectic under different temperatures and strain rates. Pronounced liquid metal embrittlement phenomenon is observed between 200 °C and 450 °C. Total elongation is reduced greatly due to the liquid metal embrittlement in LBE environment. The range of ductility trough is larger under slow strain rate tensile (SSRT) test.

This paper reports the preliminary results for an on-going program in wafer-level MEMS package. In this particular paper, three closed-loop microheaters of 5μm, 7μm and 9μm width were designed. By reactive ion sputtering technique, two classes of samples were presented. The first one was first co-sputtered with nickel / chromium (Ni/Cr) alloy and then sputtered with gold(Au) metal as heating material; the second one was sputtered with Cr, tin (Sn) and Au respectively as heating material. The bonding of the former sample based on the Ni/Cr and Au heating material failed. The eutectic bonding experiment of the later sample based on the Cr, Sn and Au heating material by global heating method was completed in annealing oven at temperature of about 400 for 20 minutes. The SEM testing result showed the eutectic bonding of Au-Sn by global heating was successful. More results will be reported in future.

This paper reports the preliminary results for an on-going program in wafer-level MEMS package. In this particular paper, three closed-loop microheaters of 5μm, 7μm and 9μm width were designed. By reactive ion sputtering technique, two classes of samples were presented. The first one was first co-sputtered with nickel / chromium (Ni/Cr) alloy and then sputtered with gold(Au) metal as heating material; the second one was sputtered with Cr, tin (Sn) and Au respectively as heating material. The bonding of the former sample based on the Ni/Cr and Au heating material failed. The eutectic bonding experiment of the later sample based on the Cr, Sn and Au heating material by global heating method was completed in annealing oven at temperature of about 400 deg. C. for 20 minutes. The SEM testing result showed the eutectic bonding of Au-Sn by global heating was successful. More results will be reported in future.

Transparent binary alloy models are important in metallurgical and materials science, as phase transformations can be observed during solidification. This communication concerns the solidification and thermal studies of succinonitrile (SCN)-pyrene (PY) system, which is an organic analogue of a metal-nonmetal-type system. Phase diagram of the SCN-PY system, determined by the thaw-melt method shows the formation of a monotectic and a eutectic at 143.3°C and 55.3°C with 0.025 and 0.744 mole fractions of SCN, respectively. The critical solution temperature of the system lies 48.7°C above the monotectic temperature. The growth velocity ( v) data at different undercoolings obtained from the capillary method, obey the Hillig-Turnbull equation, v= u(Δ T) n. The heats of fusion of the binary as well as single materials were obtained from the DSC (Mettler DSC-4000 system) from which the entropy of fusion, enthalpy of mixing, Jackson's roughness parameter, excess thermodynamic functions, interfacial energy and radius of the critical nucleus were calculated. The optical microphotographs of the eutectic and monotectic show their characteristic features.

A new model of graphite growth during the continuous cooling of eutectic spheroidal cast iron is presented in this paper. The model considers the nucleation and growth of graphite from pouring to room temperature. The microstructural model of solidification accounts for the eutectic as divorced and graphite growth rate as a function of carbon gradient at the liquid in contact with the graphite. In the solid state, the microstructural model takes into account three stages for graphite growth, namely (1) from the end of solidification to the upper bound of intercritical stable eutectoid, (2) during the intercritical stable eutectoid, and (3) from the lower bound of intercritical stable eutectoid to room temperature. The micro- and macrostructural models are coupled using a sequential multiscale approach. Numerical results for graphite fraction and size distribution are compared with experimental results obtained from a cylindrical cup, in which the graphite volumetric fraction and size distribution were obtained using the Schwartz-Saltykov approach. The agreements between the experimental and numerical results for the fraction of graphite and the size distribution of spheroids reveal the importance of numerical models in the prediction of the main aspects of graphite in spheroidal cast iron.

Polyethylene oxide (PEO) and lithium salt based solid polymer electrolytes (SPEs) have been widely proposed as a substitution for the liquid electrolyte in Li-ion batteries. As salt concentration varies, these systems demonstrate rich phase behavior. Conductivity as a function of salt concentration has been measured for decades and various concentration dependences have been observed. A PEO:LiX mixture can have one or two conductivity maximums, while some mixtures with salt of high ionic strength will have higher conductivity as the salt concentration decrease. The factors that affect the conductivity are specific for each sample. The universal factor that affects conductivity is still not clear. In this work, we measured the conductivity of a series of PEO:LiX mixtures and statistical analysis shows conductivity is affected by the concentration difference from the eutectic concentration (Δc). The correlation with Δc is stronger than the correlation with glass transition temperature. We believe that at the eutectic concentration, during the solidification process, unique structures can form which aid conduction. Currently at Dow Chemical.

This manuscript reports on research into two low-melting, lead-free solder alloys, eutectic Bi-Sn and eutectic In-Sn. The microstructures were found to depend on both cooling rate and substrate, with the greatest variability in the In-Sn alloy. The nature of the intermetallic layer formed at the solder-substrate interface depends on both the solder and the substrate (Cu versus Ni). Also, the microstructure of the Bi-Sn can recrystallize during deformation, which is not the case with In-Sn. Data from creep and constant strain rate tests are given for slowly cooled samples. The creep behavior of In-Sn is constant with temperature, but the creep seems to be controlled by the In-rich phase in In-Sn on Cu and by the Sn-rich phase in In-Sn on Ni. Bi-Sn exhibits different creep behavior at temperatures above 40 {degrees}C than at 20 {degrees}C or lower. Stress-strain curves of Bi-Sn on Cu and In-Sn on Cu are similar, while In-Sn on Ni behaves differently. This is explained in terms of the deformation patterns in the alloys.

Triolein (TO) and phospholipids (egg yolk phosphatidylcholine, egg yolk phosphatidylethanolamine, and bovine brain phosphatidylserine) had low mutual solubilities and separated into the TO-liquid phase and phospholipid-bilayers. Spreading pressures of the TO-phospholipid mixture (i.e., surface pressures of the mixed monolayer in equilibrium with the phase-separating lipid mixture) at the air/saline interface were independent of the lipid composition. On the other hand, collapse pressures of the mixed monolayer of TO and phospholipid (i.e., surface pressures of the mixed monolayer in equilibrium with the TO-liquid phase) at the interface changed with the monolayer composition and were lower than the spreading pressure. The experimental data indicated the spreading and collapse pressures as offering a phase diagram for the presence of equilibrium between the mixed monolayer, the phospholipid-bilayers and the TO-liquid phase. The diagram showed that TO and the phospholipids were miscible in the mixed monolayer, forming an eutectic mixed monolayer. When the mixed monolayer initially had the eutectic composition, no collapse of the monolayer was detected until the surface pressure reached the value of the spreading pressure. No specific complex between TO and the phospholipid is required to explain the stability and collapse of the mixed monolayers. The bulk immiscibility of the lipids elucidated by the spreading pressure-measurements, immediately leads to the phase behaviors observed. PMID:8369406

Atomic distribution in phosphors for neutron detection has not been fully elucidated, although their ionization efficiency is strongly dependent on the state of the rare earth in the matrix. In this work, we examine optical properties of Eu-doped 80LiF-20CaF2 eutectics for neutron detector applications based on the Eu distribution. At low concentrations, aggregation of Eu cations is observed, whereas homogeneous atomic dispersion in the CaF2 layer, to substitute Ca2+ ions, is observed in the eutectics at high concentrations. Eu LIII edge X-ray absorption fine structure (XAFS) analysis suggests that neutron responses do not depend on the amount of Eu2+ ions. However, transparency, which depends on an ordered lamellar structure, is found to be important for a high light yield in neutron detection. The results confirm the effectiveness of the basic idea concerning the separation of radiation absorbers and activators in particle radiation scintillation and present potential for further improvement of novel bulk detectors.

A therapeutic deep eutectic system (THEDES) is here defined as a deep eutectic solvent (DES) having an active pharmaceutical ingredient (API) as one of the components. In this work, THEDESs are proposed as enhanced transporters and delivery vehicles for bioactive molecules. THEDESs based on choline chloride (ChCl) or menthol conjugated with three different APIs, namely acetylsalicylic acid (AA), benzoic acid (BA) and phenylacetic acid (PA), were synthesized and characterized for thermal behaviour, structural features, dissolution rate and antibacterial activity. Differential scanning calorimetry and polarized optical microscopy showed that ChCl:PA (1:1), ChCl:AA (1:1), menthol:AA (3:1), menthol:BA (3:1), menthol:PA (2:1) and menthol:PA (3:1) were liquid at room temperature. Dissolution studies in PBS led to increased dissolution rates for the APIs when in the form of THEDES, compared to the API alone. The increase in dissolution rate was particularly noticeable for menthol-based THEDES. Antibacterial activity was assessed using both Gram-positive and Gram-negative model organisms. The results show that all the THEDESs retain the antibacterial activity of the API. Overall, our results highlight the great potential of THEDES as dissolution enhancers in the development of novel and more effective drug delivery systems. PMID:26586342

The effects of Lanthanum (La) concentration on the solidification parameters of the α-Al, Al-Si, and Al-Cu phases and on the microstructure, tensile, and hardness properties of eutectic Al-Si-Cu-Mg alloy were systematically investigated. The solidification parameters were examined using computer-aided cooling curve thermal analysis (CA-CCTA). The cooling curve and microstructure analysis showed that La altered the Si structure. The nucleation and growth temperatures of eutectic Si decreased when 0.3 wt.% La was added, and a high depression temperature was obtained with 1.0 wt.% La. High amounts of La considerably modified the Si structure and decreased the area and aspect ratio by 69.9 and 51%, respectively. The thermal analysis result recorded a faster freezing time with the La addition and a 36% alteration in the secondary dendrite arm spacing. Two secondary or ternary La-rich intermetallic phases were formed with needle- and plate-like structures. Furthermore, the mechanical properties were investigated by hardness and tensile tests with different La concentrations. The addition of small amounts of La (0.1 wt.%) significantly improved the ultimate tensile strength and quality index of the Al-Si-Cu-Mg alloy. In addition, the hardness value of Al-11Si-Cu increased by 7-8% with the increasing amount of La added.

A novel and facile magnetic deep eutectic solvents (DES) molecularly imprinted polymers (MIPs) for the selective recognition and separation of Bovine hemoglobin (BHb) was prepared. The new-type DES was adopted as the functional monomer which would bring molecular imprinted technology to a new direction. The amounts of DES were optimized. The obtained magnetic DES-MIPs were characterized with fourier transform infrared spectrometry (FT-IR), thermogravimetric analysis (TGA), field emission scanning electron microscope (FESEM), dynamic light scattering (DLS), elemental analysis and vibrating sample magnetometer (VSM). The results suggested that the imprinted polymers were successfully formed and possessed a charming magnetism. The maximum adsorption capability (Qmax) and dissociation constant (KL) were analyzed by Langmuir isotherms (R(2) = 0.9983) and the value were estimated to be 175.44 mg/g and 0.035 mg/mL for the imprinted particles. And the imprinted particles showed a high imprinting factor of 4.77. In addition, the magnetic DES-MIPs presented outstanding recognition specificity and selectivity so that it can be utilized to separate template protein from the mixture of proteins and real samples. Last but not least, the combination of deep eutectic solvents and molecular imprinted technology in this paper provides a new perspective for the recognition and separation of proteins. PMID:27566352

This study is devoted to providing a mechanistic rationale of coarsening induced failure in solder alloys during thermomechanical fatigue. Micromechanical modeling of cyclic deformation of eutectic tin-lead alloy was undertaken using the finite element method. The models consist of regularly arranged tin-rich and lead-rich phases, simulating the lamellar array and colony structure in a typical eutectic system. A fine structure and a coarse structure, bearing the same phase fraction but different in the aspect ratio of each lead-rich layer and in the number of lead-rich layers in each colony, are utilized for representing the microstructure before and after coarsening, respectively. Both phases are treated as elastic-plastic solids with their respective properties. For simplicity the creep effect is ignored without compromising the main objective of this study. Cyclic loading under pure shear and uniaxial conditions is modeled. It is found that both the fine and coarse structures exhibit essentially the same macroscopic stress-strain response. The coarse structure, however, shows a greater maximum effective plastic strain on a local scale throughout the deformation. The numerical result implies that, in a solder joint, a locally coarsened region may not be mechanically weaker than its surrounding, but it is subject to early damage initiation due to accumulated plasticity. Other implications regarding solder alloy failure and micromechanical modeling of two-phase materials are discussed.

A new model of graphite growth during the continuous cooling of eutectic spheroidal cast iron is presented in this paper. The model considers the nucleation and growth of graphite from pouring to room temperature. The microstructural model of solidification accounts for the eutectic as divorced and graphite growth rate as a function of carbon gradient at the liquid in contact with the graphite. In the solid state, the microstructural model takes into account three stages for graphite growth, namely (1) from the end of solidification to the upper bound of intercritical stable eutectoid, (2) during the intercritical stable eutectoid, and (3) from the lower bound of intercritical stable eutectoid to room temperature. The micro- and macrostructural models are coupled using a sequential multiscale approach. Numerical results for graphite fraction and size distribution are compared with experimental results obtained from a cylindrical cup, in which the graphite volumetric fraction and size distribution were obtained using the Schwartz-Saltykov approach. The agreements between the experimental and numerical results for the fraction of graphite and the size distribution of spheroids reveal the importance of numerical models in the prediction of the main aspects of graphite in spheroidal cast iron.

High-entropy alloys (HEAs) can have either high strength or high ductility, and a simultaneous achievement of both still constitutes a tough challenge. The inferior castability and compositional segregation of HEAs are also obstacles for their technological applications. To tackle these problems, here we proposed a novel strategy to design HEAs using the eutectic alloy concept, i.e. to achieve a microstructure composed of alternating soft fcc and hard bcc phases. As a manifestation of this concept, an AlCoCrFeNi2.1 (atomic portion) eutectic high-entropy alloy (EHEA) was designed. The as-cast EHEA possessed a fine lamellar fcc/B2 microstructure, and showed an unprecedented combination of high tensile ductility and high fracture strength at room temperature. The excellent mechanical properties could be kept up to 700°C. This new alloy design strategy can be readily adapted to large-scale industrial production of HEAs with simultaneous high fracture strength and high ductility. PMID:25160691

Atomic distribution in phosphors for neutron detection has not been fully elucidated, although their ionization efficiency is strongly dependent on the state of the rare earth in the matrix. In this work, we examine optical properties of Eu-doped 80LiF-20CaF2 eutectics for neutron detector applications based on the Eu distribution. At low concentrations, aggregation of Eu cations is observed, whereas homogeneous atomic dispersion in the CaF2 layer, to substitute Ca(2+) ions, is observed in the eutectics at high concentrations. Eu LIII edge X-ray absorption fine structure (XAFS) analysis suggests that neutron responses do not depend on the amount of Eu(2+) ions. However, transparency, which depends on an ordered lamellar structure, is found to be important for a high light yield in neutron detection. The results confirm the effectiveness of the basic idea concerning the separation of radiation absorbers and activators in particle radiation scintillation and present potential for further improvement of novel bulk detectors. PMID:26292726

This paper describes a new experimental system designed to investigate tritium mass transfer properties in materials important to fusion technology. Experimental activities were carried out at the Safety and Tritium Applied Research (STAR) facility located at the Idaho National Laboratory (INL). The tritium permeation measurement system was developed as part of the Japan/US TITAN collaboration to investigate tritium mass transfer properties in liquid lead lithium eutectic (LLE) alloy. The experimental system is configured to measure tritium mass transfer properties at low tritium partial pressures. Initial tritium permeation scoping tests were conducted on a 1 mm thick α-Fe plate to determinemore » operating parameters and to validate the experimental technique. A second series of permeation tests was then conducted with the α-Fe plate covered with an approximately 8.5 mm layer of liquid lead lithium eutectic alloy (α-Fe/LLE). We present preliminary tritium permeation data for α-Fe and α-Fe/LLE at temperatures between 400 and 600°C and at tritium partial pressures between 1.7E-3 and 2.5 Pa in helium. Preliminary results for the α-Fe plate and α-Fe/LLE indicate that the data spans a transition region between the diffusion-limited regime and the surface-limited regime. In conclusion, additional data is required to determine the existence and range of a surface-limited regime.« less

This paper describes a new experimental system designed to investigate tritium mass transfer properties in materials important to fusion technology. Experimental activities were carried out at the Safety and Tritium Applied Research (STAR) facility located at the Idaho National Laboratory (INL). The tritium permeation measurement system was developed as part of the Japan/US TITAN collaboration to investigate tritium mass transfer properties in liquid lead lithium eutectic (LLE) alloy. The experimental system is configured to measure tritium mass transfer properties at low tritium partial pressures. Initial tritium permeation scoping tests were conducted on a 1 mm thick α-Fe plate to determine operating parameters and to validate the experimental technique. A second series of permeation tests was then conducted with the α-Fe plate covered with an approximately 8.5 mm layer of liquid lead lithium eutectic alloy (α-Fe/LLE). We present preliminary tritium permeation data for α-Fe and α-Fe/LLE at temperatures between 400 and 600°C and at tritium partial pressures between 1.7E-3 and 2.5 Pa in helium. Preliminary results for the α-Fe plate and α-Fe/LLE indicate that the data spans a transition region between the diffusion-limited regime and the surface-limited regime. In conclusion, additional data is required to determine the existence and range of a surface-limited regime.

Creep deformation behavior was measured for 60--100 {micro}m thick solder joints. The solder joints investigated consisted of: (1) non-composite solder joints made with eutectic Sn-Ag solder, and (2) composite solder joints with eutectic Sn-Ag solder containing 20 vol.%, 5 {micro}m diameter in-situ Cu{sub 6}Sn{sub 5} intermetallic reinforcements. All creep testing in this study was carried out at room temperature. Qualitative and quantitative assessment of creep deformation was characterized on the solder joints. Creep deformation was analyzed using a novel mapping technique where a geometrical-regular line pattern was etched over the entire solder joint using excimer laser ablation. During creep, the laser-ablation (LA) pattern becomes distorted due to deformation in the solder joint. By imaging the distortion of laser-ablation patterns using the SEM, actual deformation mapping for the entire solder joint is revealed. The technique involves sequential optical/digital imaging of the deformation versus time history during creep. By tracing and recording the deformation of the LA patterns on the solder over intervals of time, local creep data are obtained in many locations in the joint. This analysis enables global and localized creep shear strains and strain rate to be determined.

Natural deep eutectic solvents (DESs) dissolve simple metal oxides and are used as a reaction medium to synthesize spinel-type ferrite nanoparticles MFe2 O4 (M=Mg, Zn, Co, Ni). The best results for phase-pure spinel ferrites are obtained with the DES consisting of choline chloride (ChCl) and maleic acid. By employing DESs, the reactions proceed at much lower temperatures than usual for the respective solid-phase reactions of the metal oxides and at the same temperatures as synthesis with comparable calcination processes using metal salts. The method therefore reduces the overall required energy for the nanoparticle synthesis. Thermogravimetric analysis shows that the thermolysis process of the eutectic melts in air occurs in one major step. The phase-pure spinel-type ferrite particles are thoroughly characterized by X-ray diffraction, diffuse-reflectance UV/Vis spectroscopy, and scanning electron microscopy. The properties of the obtained nanoparticles are shown to be comparable to those obtained by other methods, illustrating the potential of natural DESs for processing metal oxides. PMID:27514793

The quasi-binary eutectic NiAl-9% Mo with faceted molybdenum fibers was subjected to both thermal annealing conditions and to annealing under thermal cycling conditions to determine the microstructural stability of this alloy. The static temperature tests were run at 0.85T{sub M}--0.97T{sub M} in an argon gas atmosphere. The thermal cycling tests were performed between temperatures of 700 C and 1,200 C by induction heating disk-shaped specimens in an argon gas atmosphere using time-temperature heating and cooling profiles to approximate potential engine applications. To quantify microstructural changes, the fiber size and size distribution and number of fibers per unit area were measured as a function of time at temperature. The overall results demonstrate that the directionally solidified eutectic NiAl-9Mo subjected to thermal fatigue conditions exhibits cell boundary coarsening and large shape changes, whereas the microstructure under static stress-free annealing is stable.

The effects of Lanthanum (La) concentration on the solidification parameters of the α-Al, Al-Si, and Al-Cu phases and on the microstructure, tensile, and hardness properties of eutectic Al-Si-Cu-Mg alloy were systematically investigated. The solidification parameters were examined using computer-aided cooling curve thermal analysis (CA-CCTA). The cooling curve and microstructure analysis showed that La altered the Si structure. The nucleation and growth temperatures of eutectic Si decreased when 0.3 wt.% La was added, and a high depression temperature was obtained with 1.0 wt.% La. High amounts of La considerably modified the Si structure and decreased the area and aspect ratio by 69.9 and 51%, respectively. The thermal analysis result recorded a faster freezing time with the La addition and a 36% alteration in the secondary dendrite arm spacing. Two secondary or ternary La-rich intermetallic phases were formed with needle- and plate-like structures. Furthermore, the mechanical properties were investigated by hardness and tensile tests with different La concentrations. The addition of small amounts of La (0.1 wt.%) significantly improved the ultimate tensile strength and quality index of the Al-Si-Cu-Mg alloy. In addition, the hardness value of Al-11Si-Cu increased by 7-8% with the increasing amount of La added.

The challenges associated with synthesizing porous materials mean that new classes of zeolites (zeotypes)-such as aluminosilicate zeolites and zeolite analogues-together with new methods of preparing known zeotypes, continue to be of great importance. Normally these materials are prepared hydrothermally with water as the solvent in a sealed autoclave under autogenous pressure. The reaction mixture usually includes an organic template or 'structure-directing agent' that guides the synthesis pathway towards particular structures. Here we report the preparation of aluminophosphate zeolite analogues by using ionic liquids and eutectic mixtures. An imidazolium-based ionic liquid acts as both solvent and template, leading to four zeotype frameworks under different experimental conditions. The structural characteristics of the materials can be traced back to the solvent chemistry used. Because of the vanishingly low vapour pressure of ionic liquids, synthesis takes place at ambient pressure, eliminating safety concerns associated with high hydrothermal pressures. The ionic liquid can also be recycled for further use. A choline chloride/urea eutectic mixture is also used in the preparation of a new zeotype framework. PMID:15329717

Atomic distribution in phosphors for neutron detection has not been fully elucidated, although their ionization efficiency is strongly dependent on the state of the rare earth in the matrix. In this work, we examine optical properties of Eu-doped 80LiF-20CaF2 eutectics for neutron detector applications based on the Eu distribution. At low concentrations, aggregation of Eu cations is observed, whereas homogeneous atomic dispersion in the CaF2 layer, to substitute Ca2+ ions, is observed in the eutectics at high concentrations. Eu LIII edge X-ray absorption fine structure (XAFS) analysis suggests that neutron responses do not depend on the amount of Eu2+ ions. However, transparency, which depends on an ordered lamellar structure, is found to be important for a high light yield in neutron detection. The results confirm the effectiveness of the basic idea concerning the separation of radiation absorbers and activators in particle radiation scintillation and present potential for further improvement of novel bulk detectors. PMID:26292726

Natural deep eutectic solvents (NADES) are a newly discovered group of eutectics which has shown promise as a solvent in antimicrobial photodynamic therapy (aPDT). The purpose of this study was to investigate preparations of an anionic porphyrin, meso-tetra-(4-carboxyphenyl)-porphine (TCPP), solubilised in NADES, with regard to their physicochemical and antibacterial properties. The NADES CS (pH∼0), ChX (pH∼4) and MFG (pH∼1) solubilised TCPP with absorption maximum ∼443nm and emission maximum ∼678nm, indicating formation of the TCPP dication. Dilution of TCPP-NADES>1:1 (water) reduced the physical stability of the preparations. The photostability half-lives of TCPP in methanol, MFG, and CS were ∼9h, 6.9h and 3.2h, respectively. Nanomolar concentrations of TCPP solubilised in diluted MFG combined with ⩽27J/cm(2) blue light increased Gram-positive and Gram-negative bacterial phototoxicity, >99.98% and 96% bacterial reduction, respectively, compared to TCPP in PBS/ethanol under equivalent treatment conditions. TCPP solubilised in diluted CS was toxic to bacteria both in the absence (36-72% reduction) and presence of light. TCPP in CS, and in the CS component citric acid, induced a TCPP-concentration dependent increase in Gram-negative phototoxicity relative to controls, which was most pronounced for TCPP-CS. The mechanism behind the increased toxicity is unknown. PMID:27269504

Ternary eutectics, where three phases form simultaneously from the melt, present an opportunity to study the fundamental science of microstructural pattern formation during the process of solidification. In this paper we investigate these phenomena, both experimentally and by phase-field simulations. The aim is to develop necessary characterisation tools which can be applied to both experimentally determined and simulated microstructures for a quantitative comparison between simulations and experiments. In SEM images of experimental cross sections of directionally solidified Ag-Al-Cu ternary eutectic alloy at least six different types of microstructures are observed. Corresponding 3D phase-field simulations for different solidification conditions and compositions allow us to span and isolate the material parameters which influence the formation of three-phase patterns. Both experimental and simulated microstructures were analysed regarding interface lengths, triple points and number of neighbours. As a result of this integrated experimental and computational effort we conclude that neighbourhood relationships as described herein, turn out to be an appropriate basis to characterise order in patterns.

The structure of molten eutectic Al87.8Si12.2 alloy has been studied by neutron diffraction during a temperature cycle. For comparison measurements were performed on pure molten Al. The measurements show that the alloy after heating above the liquidus contains particles of two kinds, aluminum-rich and silicon-rich. The silicon-rich particles are partly dissolved after a further heating. Earlier published data obtained by the γ-ray absorption technique of the density of the molten eutectic Al–Si alloy had demonstrated the existence of two temperatures above the liquidus temperature: A dissolution temperature Td, at which the microstructure of the melt inherited from the ingot starts to dissolve and a branching temperature, Tb, at which the melt reaches a fully mixed state. The highest temperature that was possible to reach during the neutron experiments lies between Td and Tb. The obtained results support these conclusions that molten alloys after melting are inhomogeneous up to a temperature well above the liquidus. Moreover, the difference in shape between the static structure factors measured by neutron and X-ray diffraction on molten aluminum is observed and is found to be more accentuated and to extend to larger wavevectors than in earlier works.

Excessive fuel assembly vibrations in nuclear reactor cores should be avoided in order not to compromise the lifetime of the assembly and in order to prevent the occurrence of safety hazards. This issue is particularly relevant to new reactor designs that use liquid metal coolants, such as, for example, a molten lead-bismuth eutectic. The flow of molten heavy metal around and through the fuel assembly may cause the latter to vibrate and hence suffer degradation as a result of, for example, fretting wear or mechanical fatigue. In this paper, we demonstrate the use of optical fiber sensors to measure the fuel assembly vibration in a lead-bismuth eutectic cooled installation which can be used as input to assess vibration-related safety hazards. We show that the vibration characteristics of the fuel pins in the fuel assembly can be experimentally determined with minimal intrusiveness and with high precision owing to the small dimensions and properties of the sensors. In particular, we were able to record local strain level differences of about 0.2 μϵ allowing us to reliably estimate the vibration amplitudes and modal parameters of the fuel assembly based on optical fiber sensor readings during different stages of the operation of the facility, including the onset of the coolant circulation and steady-state operation. PMID:27110782

Oxide eutectics offer high-temperature strength retention and creep resistance in oxidizing environments. Al2O3-ZrO2 eutectic strengths have been studied since the 1970's. Directionally solidified oxide eutectics exhibit improved resistance to slow crack growth and excellent strength retention at high temperatures up to 1400 C. Materials studied typically contain Y2O3 to metastably retain the high-temperature cubic and tetragonal polymorphs at room temperature. Al2O3-ZrO2 is of fundamental interest for creep studies because it combines a creep-resistant material, Al2O3, with a very low creep resistance material, ZrO2. Results on mechanical properties and microstructures of these materials will be used to define compositions for creep testing in future work. Substantial variations from the eutectic alumina to zirconia ratio can be tolerated without a loss in room-temperature strength. The effect of increasing Y2O3 addition on the room-temperature tensile strength of an Al2O3-ZrO2 material containing excess Al2O3 was examined at the NASA Glenn Research Center, where the materials were grown using Glenn's world-class laser growth facilities.

Although the vapor-liquid-solid growth of semiconductor nanowire is a non-equilibrium process, the equilibrium phase diagram of binary alloy provides important guidance on the growth conditions, such as the temperature and the equilibrium composition of the alloy. Given the small dimensions of the alloy seeds and the nanowires, the known phase diagram of bulk binary alloy cannot be expected to accurately predict the behavior of the nanowire growth. Here, we developed a unified model to describe the size- and dimensionality-dependent equilibrium phase diagram of Au-Ge binary eutectic nanoalloys based on the size-dependent cohesive energy model. It is found that the liquidus curves reduce and shift leftward with decreasing size and dimensionality. Moreover, the effects of size and dimensionality on the eutectic composition are small and negligible when both components in binary eutectic alloys have the same dimensionality. However, when two components have different dimensionality (e.g. Au nanoparticle-Ge nanowire usually used in the semiconductor nanowires growth), the eutectic composition reduces with decreasing size. PMID:26053237

Deep Eutectic Solvents (DESs) based upon mixtures of Acrylic Acid (AA) or Methacrylic Acid (MAA) and Choline Chloride (CCl) demonstrated superior performance than regular organic solvents and even ionic liquids for frontal polymerizations (FPs). Full recovering of CCl after FP provided an interesting green character to the process. PMID:21455538

In the present investigation, microstructural evolutions of functionally graded eutectic Al-Cu strips prepared by high-speed twin-roll strip caster at different casting speeds and liquid melt superheats were studied. The as-cast sample was subjected to scanning electron microscope to study the evolution of microstructure of the strip at different casting speeds and liquid melt superheats. At different casting speeds, non-equilibrium eutectic structure observed on the Al-Cu eutectic strip consists of lamellar as well as wavy structure with a distinct boundary. The lamellar microstructure consists of alternating layers of well-bonded α-Al phase and θ-Al2Cu phase. The globular flowery structure within the eutectic matrix was observed on the strip at different liquid melt superheats. The microhardness of the as-cast strip was studied by Vickers hardness tester, and it was found that hardness value increases with increasing casting speed and decreases with increasing liquid melt superheat.

Free sugars reacted with acetic anhydride in a deep eutectic solvent made from choline chloride and ZnCl2 at 90 °C to afford the corresponding peracetates that on further heating to 100 °C underwent selective deacetylation at the anomeric position to furnish the corresponding peracetylated hemiacetals in good yield. PMID:26335374

The effect of a high magnetic field on the morphology of the Al-Si eutectic was investigated using EBSD technology. The results revealed that the application of the magnetic field modified the morphology of the Al-Si eutectic significantly. Indeed, the magnetic field destroyed the coupled growth of the Al-Si eutectic and caused the formation of the divorced α-Al and Si dendrites at low growth speeds (≤1 μm/s). The magnetic field was also found to refine the eutectic grains and reduce the eutectic spacing at the initial growth stage. Moreover, the magnetic field caused the occurrence of the columnar-to-equiaxed transition of the α-Al phase in the Al-Si eutectic. The abovementioned effects were enhanced as the magnetic field increased. This result should be attributed to the magnetic field restraining the interdiffusion of Si and Al atoms in liquid ahead of the liquid/solid interface and the thermoelectric magnetic force acting on the eutectic lamellae under the magnetic field.

The effect of a high magnetic field on the morphology of the Al-Si eutectic was investigated using EBSD technology. The results revealed that the application of the magnetic field modified the morphology of the Al-Si eutectic significantly. Indeed, the magnetic field destroyed the coupled growth of the Al-Si eutectic and caused the formation of the divorced α-Al and Si dendrites at low growth speeds (≤1 μm/s). The magnetic field was also found to refine the eutectic grains and reduce the eutectic spacing at the initial growth stage. Moreover, the magnetic field caused the occurrence of the columnar-to-equiaxed transition of the α-Al phase in the Al-Si eutectic. The abovementioned effects were enhanced as the magnetic field increased. This result should be attributed to the magnetic field restraining the interdiffusion of Si and Al atoms in liquid ahead of the liquid/solid interface and the thermoelectric magnetic force acting on the eutectic lamellae under the magnetic field.

A slight modification of a package to transport solid metal contents requires inclusion of a thin titanium liner to protect against possible eutectic formation in 10 CFR 71.74 regulatory fire accident conditions. Under severe transport regulatory impact conditions, the package contents could impart high localized loading of the liner, momentarily pinching it between the contents and the thick containment vessel, and inducing some plasticity near the contact point. Actuator and drop table testing of simulated contents impacts against liner/containment vessel structures nearly bounded the potential plastic strain and stress triaxiality conditions, without any ductile tearing of the eutectic barrier. Additional bounding was necessary in some cases beyond the capability of the actuator and drop table tests, and in these cases a stress-modified evolution integral over the plastic strain history was successfully used as a failure criterion to demonstrate that structural integrity was maintained. The Heaviside brackets only allow the evolution integral to accumulate value when the maximum principal stress is positive, since failure is never observed under pure hydrostatic pressure, where the maximum principal stress is negative. Detailed finite element analyses of myriad possible impact orientations and locations between package contents and the thin eutectic barrier under regulatory impact conditions have shown that not even the initiation of a ductile tear occurs. Although localized plasticity does occur in the eutectic barrier, it is not the primary containment boundary and is thus not subject to ASME stress allowables from NRC Regulatory Guide 7.6. These analyses were used to successfully demonstrate that structural integrity of the eutectic barrier was maintained in all 10 CFR 71.73 and 71.74 regulatory accident conditions. The NRC is currently reviewing the Safety Analysis Report.

Monovariant eutectic alloys, located on the liquidus trough between the binary eutectic gamma, Ni - delta, Ni3Cb and the ternary eutectic gamma, Ni - gamma-prime, Ni3Al - delta, Ni3Cb, were identified which permitted the production of aligned lamellae within a nickel solid solution matrix containing the precipitate gamma-prime. These alloys exhibited great insensitivity in their composite microstructures to solidification parameters such as growth rate temperature gradient, and were found to be remarkably uniform in composition along their length.

The solidification and convection of the pure binary eutectic silicate system diopside-anorthite (Di-An) is numerically modeled. A mass-weighted enthalpy of fusion is used to account for the second solid phase (An) which crystallizes at the solidus temperature. Variable under-relaxation is used to aid convergence of the momentum equations in the implementation of the SIMPLER algorithm used to solve the two-dimensional continuum conservation equations. Numerical experiments of the solidification of Di80 melt show that a large temperature drop occurs across the solid and mush regions which decreases convective vigor in the liquid. Interesting compositional segregation patterns are produced during the solidification of Di80.

A certain combination of natural products in the solid state becomes liquid, so called natural deep eutectic solvents (NADES). Recently, they have been considered promising new green solvents for foods, cosmetics and pharmaceuticals due to their unique solvent power which can dissolve many non-water-soluble compounds and their low toxicity. However, in addition to the features as solvents, the stabilisation ability of NADES for compounds is important for their further applications. In the study, the stability analysis demonstrates that natural pigments from safflower are more stable in sugar-based NADES than in water or 40% ethanol solution. Notably, the stabilisation capacity of NADES can be adjusted by reducing water content with increasing viscosity. The strong stabilisation ability is due to the formation of strong hydrogen bonding interactions between solutes and NADES molecules. The stabilising ability of NADES for phenolic compounds shows great promise for their applications in food, cosmetic and pharmaceutical industries. PMID:24767033

Previously it was demonstrated that natural deep eutectic solvents (NADES) are promising green solvents for the extraction of natural products. However, despite their potential, an obvious disadvantage of NADES is the high viscosity. Here we explored the dilution effect on the structures and physicochemical properties of NADES and their improvements of applications using quercetin and carthamin. The results of FT-IR and (1)H NMR experiments demonstrated that there are intensive H-bonding interactions between the two components of NADES and dilution with water caused the interactions weaken gradually and even disappeared completely at around 50% (v/v) water addition. A small amount of water could reduce the viscosity of NADES to the range of water and increase the conductivity by up to 100 times for some NADES. This study provides the basis for modulating NADES in a controllable way for their applications in food processing, enzyme reactions, pharmaceuticals and cosmetics. PMID:25976992

A capacitive absolute pressure sensor was fabricated using a large deflected diaphragm with a sealed vacuum cavity formed by removing handling silicon wafer and oxide layers from a SOI wafer after eutectic bonding of a silicon wafer to the SOI wafer. The deflected displacements of the diaphragm formed by the vacuum cavity in the fabricated sensor were similar to simulation results. Initial capacitance values were about 2.18pF and 3.65pF under normal atmosphere, where the thicknesses of the diaphragm used to fabricate the vacuum cavity were 20 µm and 30 µm, respectively. Also, it was confirmed that the differences of capacitance value from 1000hPa to 5hPa were about 2.57pF and 5.35pF, respectively.

Charge transport and structural dynamics in the 1:2 mol ratio mixture of lidocaine and decanoic acid (LID-DA), a model deep eutectic mixture (DEM), have been characterized over a wide temperature range using broad-band dielectric spectroscopy and depolarized dynamic light scattering. Additionally, Fourier transform infrared spectroscopy measurements were performed to assess the degree of proton transfer between the neutral parent molecules. From our detailed analysis of the dielectric spectra, we have determined that this carboxylic-acid-based DEM is approximately 25% ionic at room temperature. Furthermore, we have found that the characteristic diffusion rate of mobile charge carriers is practically identical to the rate of structural relaxation at all measured temperatures, indicating that fast proton transport does not occur in LID-DA. Our results demonstrate that while LID-DA exhibits the thermal characteristics of a DEM, its charge transport properties resemble those of a protic ionic liquid. PMID:25025600

Density, viscosity and ionic conductivity data sets of deep eutectic solvents (DESs) formed by tetrabutylammonium bromide (TBABr) paired with ethlyene glycol, 1,3-propanediol, 1,5-pentanediol and glycerol hydrogen bond donors (HBDs) are reported. The properties of DES were measured at temperatures between 303 K and 333 K for HBD percentages of 66.7% to 90%. The effects of HBDs under different temperature and percentages are systematically analyzed. As expected, the measured density and viscosity of the studied DESs decreased with an increase in temperature, while ionic conductivity increases with temperature. In general, DESs made of TBABr and glycerol showed the highest density and viscosity and the lowest ionic conductivity when compared to other DESs. The presence of an extra hydroxyl group on glycerol in a DES affected the properties of the DES. PMID:24932572

There is an ongoing interest at the US Department of Energy in using molten salts as high temperature sensible heat storage media in advanced solar thermal systems. In this report, the compatibility of selected alloys in eutectic lithium-sodium-potassium carbonate, the salt that will be used in the near-term engineering experiments, has been evaluated at 900C. Several combinations of oxidation potential and acidity in the salt were used in the experiments. It was found that the extent of corrosion was dramatically lower for experiments conducted at high oxygen potential compared to experiments at low oxygen potential. For Inconel 600, Hastelloy N, and nickel the results indicated that corrosion rates substantially below 1 mm/year/side might reasonably be expected and that a reevaluation of alloys the showed poor corrosion resistance under low oxygen potential would be advisable.

Eutectic superalloys are being developed at several laboratories for application as aircraft gas turbine airfoils. One such alloy was subjected to several heat treatments to determine if its mechanical properties could be improved. It was found that by partially dissolving the alloy at 1210 C and then aging at 900 C the tensile strength can be increased about 12 percent at temperatures up to 900 C. At 1040 C no change in tensile strength was observed. Times to rupture were measured between 760 and 1040 C and were essentially the same or greater than for as-grown material. Tensile and rupture ductility of the alloy are reduced by heat treatment. Photographs of the microstructure are shown.

Eutectic superalloys are being developed at several laboratories for application as aircraft gas turbine airfoils. One such alloy gamma/gamma prime + delta was subjected to several heat treatments to determine if its mechanical properties could be improved. It was found that by partially dissolving the gamma prime at 1210 C and then aging at 900 C, the tensile strength can be increased about 12 per cent at temperatures up to 900 C. At 1040 C, no change in tensile strength was observed. Times to rupture were measured between 760 and 1040 C and were essentially the same or greater than for as-grown material. Tensile and rupture ductility of the alloy were reduced by heat treatment.

Potato starch and high-amylose starch were treated with imidazole-based deep eutectic solvents (DESs) as dissolution and plasticization media. Beside imidazole (IM) for two-component DESs preparation choline chloride (CC), glycerol (G) or carboxylic acids (citric or malic) were used. An influence of water content in starch (as well as an extra water in the starch/DES system) on polymer dissolution and plasticization processes was investigated. Dissolution and gelatinization of starch in DESs were followed via DSC and laser scanning microscopy. A rheometric characteristics revealed an influence of starch/DES system storage time on the plasticization process. The tendency to recrystallization of compression-molded-starch films was evaluated using XRD technique. High dissolution and plasticization effectiveness of CC/IM and G/IM and a low tendency to film retrogradation of thermoplasticized starch were noted. PMID:26876869

Watson and Haff (1980) have discussed a theory which is designed to explain quantitatively isotopic fractionation effects observed during sputtering of simple or complex targets. This theory is based on the assumption that most of the atoms sputtered from a surface originate in the top monolayer. The present investigation is mainly concerned with a direct experimental test of that assumption. The sputtering of both solid and liquid phases of gallium, indium, and the gallium-indium eutectic alloy is studied. Results obtained with the aid of ion scattering and Auger spectroscopy show that, in agreement with rough theoretical expectations, the surface monolayer of a gallium-indium alloy with 16.5 percent indium in bulk contains more than 94 percent indium, while the next layer can be only slightly enriched.

Samples of rod eutectics Bi/MnBi were directionally solidified in a growth-up Bridgman-Stockbarger configuration in the presence of a transverse magnetic field up to 3 kg to determine whether gravity-driven convective effects could be reduced or eliminated. The experiments were carried out over a range of furnace velocities, V, of 0.2 to 50 cm per hour with a thermal gradient at the liquid-solid interface of 100 C/cm and 150 C/cm. Morphological, thermal and magnetic analyses were carried out on samples grown with and without an applied magnetic field. For samples grown at V greater than 3 cm per hour in a transverse magnetic field, reduced mean rod diameter and interrod spacing occurred as well as undercooling and increased coercive strength. The data agreed with that obtained for low-g growth at 50 cm per hour and 30 cm per hour.

A two dimensional model developed to study the influence of convective flow on the concentration field ahead of a growing lamellar eutectic is described when one phase projects out into the melt creating a stepped interface. The two dimensional convective flow field, which is periodic in the horizontal direction, was computed numerically using the software FLUENT. The velocity field generated due to the flow of melt over the steps was then incorporated into a finite difference scheme employed to solve the concentration field. The average interfacial composition was calculated and converted to lamellar spacing using the Jackson and Hunt minimum supercooling criterion. It was found that a stepped interface is more sensitive to convection than a planar interface.

Directional solidification of MnBiBi eutectic in space produced MnBi fibers that were significantly finer and closer together than when solidification was carried out on earth under otherwise identical conditions. Use of a strong magnetic field during solidification on earth gave about the same results as solidification in space, indicating that convection is the cause of the difference in microstructure. However, 15 years of theoretical and experimental research have failed to reveal the mechanism for this phenomenon. It has been found that temperature gradient has no effect; the concentration field in front of the freezing interface is not altered sufficiently by buoyancy-driven convection to explain it, even if the MnBi fibers project out in front of the Bi matrix; and the Soret effect is not sufficiently large. On the other hand, vigorous forced convection caused a change in microstructure in agreement with theory.

A two dimensional model developed to study the influence of convective flow on the concentration field ahead of a growing lamellar eutectic is described when one phase projects out into the melt creating a stepped interface. The two dimensional convective flow field, which is periodic in the horizontal direction, was computed numerically using the software FLUENT. The velocity field generated due to the flow of melt over the steps was then incorporated into a finite difference scheme employed to solve the concentration field. The average interfacial composition was calculated and converted to lamellar spacing using the Jackson and Hunt minimum supercooling criterion. It was found that a stepped interface is more sensitive to convection than a planar interface.

The electrolysis of plutonium nitride, PuN, was investigated in the LiCl-KCl eutectic salt with 0.54 wt% PuCl 3 at 773 K in order to understand the dissolution of PuN at the anode and the deposition of metal at the cathode from the viewpoint of the application of a pyrochemical process to nitride fuel cycle. It was found from cyclic voltammetry that the electrochemical dissolution of PuN began nearly at the theoretically evaluated potential and this reaction was irreversible. Several grams of plutonium metal were successfully recovered at the molybdenum electrode as a deposit with a current efficiency of about 90%, although some fractions of the deposited plutonium often fell from the molybdenum electrode.

We have investigated the growth of iron disilicide on Au-coated Si(0 0 1) substrates and its photoluminescence behaviour. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy observations revealed that the Si surface above 380 °C was melted as a result of the Au-Si eutectic reaction and that coarse island disilicide grains with sizes of several micrometres were formed on the Si surface. The full width at half maximum of 0.056° on the rocking curve of α-FeSi 2004 was observed on the sample deposited at 800 °C, and indicated the high crystal quality in perfection of orientation. The photoluminescence spectrum of β-FeSi 2 grains, which were deposited at 750 °C, was observed. The melted Si surface contributed to the improved crystallinity of α-FeSi 2 and β-FeSi 2.

Deep Eutectic Solvents (DES) can be formed between a variety of quaternary ammonium salts and carboxylic acids. The physical properties are significantly affected by the structure of the carboxylic acid but the phase behavior of the mixtures can be simply modeled by taking account of the mole fraction of carboxylic acid in the mixture. The physical properties such as viscosity, conductivity, and surface tension of these DES are similar to ambient temperature ionic liquids and insight into the cause of these properties is gained using hole-theory. It is shown that the conductivity and viscosity of these liquids is controlled by ion mobility and the availability of voids of suitable dimensions, and this is consistent with the fluidity of other ionic liquids and molten salts. The DES are also shown to be good solvents for metal oxides, which could have potential application for metal extraction. PMID:15264850

A new mechanism for twin nucleation in the eutectic Al-Si alloy with trace Sr impurities is proposed. Observations made by sub-angstrom resolution scanning transmission electron microscopy and X-ray probing proved the presence of <110> Sr columns located preferentially at twin boundaries. Density functional theory simulations indicate that Sr atoms bind in the Si lattice only along the <110> direction, with preferential positions at first and second nearest neighbors for interstitial and substitutional Sr, respectively. Density functional theory total energy calculations confirm that twin nucleation at Sr columns is energetically favorable. Hence, twins may nucleate in Si precipitates after solidification, which provides a different perspective to the currently accepted mechanism which suggests twin formation during precipitate growth. PMID:27527789

The effects of thermal and solute gradient, gravity induced convection during vertical directional solidification, on longitudinal macrosegregation of Bi and Mn rich off-eutectic starting compositions, has been studied as a function of composition, growth velocity and gravity vector orientation. Since the morphology of these alloys is characterized by an aligned, rodlike permanent magnet composite when grown cooperatively, the magnetic properties were used to measure composition segregation and the transition from dendritic to composite growth. Severe macrosegregation was observed in all cases studied and the degree of convection inferred by modeling the observed composition segregation using a stagnant film approach. Morphological stability was found to follow a constitutional supercooling-type law for both Bi and Mn rich compositions.

A new mechanism for twin nucleation in the eutectic Al-Si alloy with trace Sr impurities is proposed. Observations made by sub-angstrom resolution scanning transmission electron microscopy and X-ray probing proved the presence of <110> Sr columns located preferentially at twin boundaries. Density functional theory simulations indicate that Sr atoms bind in the Si lattice only along the <110> direction, with preferential positions at first and second nearest neighbors for interstitial and substitutional Sr, respectively. Density functional theory total energy calculations confirm that twin nucleation at Sr columns is energetically favorable. Hence, twins may nucleate in Si precipitates after solidification, which provides a different perspective to the currently accepted mechanism which suggests twin formation during precipitate growth. PMID:27527789

A program was performed to scale up the edge-defined, film-fed growth (EFG) method for the gamma/gamma prime-beta eutectic alloy of the nominal composition Ni-19.7 Cb - 6 Cr-2.5 Al. Procedures and problem areas are described. Flat bars approximately 12 x 1.7 x 200 mm were grown, mostly at speeds of 38 mm/hr, and tensile tests on these bars at 25 and 1000 C showed lower strength than expected. The feasibility of growing hollow airfoils was also demonstrated by growing bars over 200 mm long with a teardrop shaped cross-section, having a major dimension of 12 mm and a maximum width of 5 mm.

Extensive in situ thermal measurements using Peltier Interface Demarcation (PID) during directional solidification of eutectic Bi/MnBi were carried out. Observations indicate that significant thermal transients occur throughout the sample as a result of the Peltier pulsing. The contributions of the Peltier, Thomson, and Joule heats were separated and studied as a function of pulse intensity and polarity. The Joule and the combined Peltier and Thomson thermal contributions were determined as a function of time during and after the current pulses, close to the solid/liquid interface. Variations of the Bi/MnBi particle morphology clearly reveal the interface shape, changes in interface velocity, meltback, and temporary loss of cooperative growth, as a result of the pulsing.

Conventional extraction techniques for plant phenolics are usually associated with high organic solvent consumption and long extraction times. In order to establish an environmentally friendly extraction method for grape skin phenolics, deep eutectic solvents (DES) as a green alternative to conventional solvents coupled with highly efficient microwave-assisted and ultrasound-assisted extraction methods (MAE and UAE, respectively) have been considered. Initially, screening of five different DES for proposed extraction was performed and choline chloride-based DES containing oxalic acid as a hydrogen bond donor with 25% of water was selected as the most promising one, resulting in more effective extraction of grape skin phenolic compounds compared to conventional solvents. Additionally, in our study, UAE proved to be the best extraction method with extraction efficiency superior to both MAE and conventional extraction method. The knowledge acquired in this study will contribute to further DES implementation in extraction of biologically active compounds from various plant sources. PMID:26830574

Electromigration has emerged as an important reliability issue in the microelectronics packaging industry since the dimension of solder joints has continued to shrink. In this letter, we report a technique that enables the precise measurement of the important parameters of solder electromigration, such as activation energy, critical length, threshold current density, effective charge numbers, and electromigration rate. Patterned Cu/Ti films in a Si trench were employed for eutectic SnPb solder to be reflowed on, and thus solder Blech specimens were fabricated. Atomic force microscope was used to measure the depletion volume caused by electromigration on the cathode end. The threshold current density is estimated to be 8.5x10{sup 3} A/cm{sup 2} at 100 deg. C, which relates directly to the maximum allowable current that a solder joint can carry without electromigration damage. This technique facilitates the scientifically systematic investigation of electromigration in solders.

Efforts to identify and characterize the physical properties of aluminum castings alloys are envisaged to lead to a new guideline from which the mechanical behavior of these alloys can be accurately predicted. For aluminum-silicon (Al-Si) casting alloys the tensile properties of a specific composition are observed to vary depending on the production parameters. The difference in the tensile properties appears to be mainly due to the microstructural features concomitant with the imposed production parameters. The present study aims to identify, quantitatively, the tensile properties influencing variables in high purity eutectic Al-Si casting alloy produced under a variety of solidification cooling rate with different strontium (Sr) additions, as a modifying agent. The correlation between the fracture characteristics and the microstructures has also been investigated.

The relationship between the process variables and the property of oxidation resistance was investigated for aluminide-coated γ'/δ directional eutectics by the control of the surface composition and the coating microstructure. The oxidation behavior of coated and uncoated substrates was found to belong to three main groups, depending on the surface composition of the coated or uncoated substrate prior to oxidation and irrespective of the manner in which the coating was processed. The coatings with surface composition in Group I formed protective external scales of A12O3; those with surface compositions in Group II formed nonprotective external scales of niobium-rich oxides; those substrates with surface compositions in Group III formed nonprotective external scales of NiO. The oxidation behavior within each group is herein explained in terms of the coating microstructure. Coatings that possessed a single-phase surface layer demonstrated better oxidation resistance than those with a two-phase lamellar morphology.

We describe a method to measure the free-energy difference, DeltaG, between crystal polymorphs from their calorimetric data of eutectic melting with a common additive. The use of different additives yields DeltaG as a function of temperature. The method is suitable for crystals that chemically decompose or physically transform before melting. It applies to not only true polymorphs but also pairs of racemate and conglomerate of resolvable enantiomers. We illustrate the method with the polymorphs of glycine, d-mannitol, and tazofelone and report a new value (123 degrees C) for the enantiotropic transition temperature of alpha and gamma glycine. We show how different additives (including a liquid additive, water) can be used for different compounds. The DeltaG data thus obtained are important for structure-stability studies and controlling crystallization in polymorphic systems. PMID:16853575

The aim of this review is to provide an exposition of some of the most recent applications of deep-eutectic solvents (DESs) in the synthesis of polymers and related materials. We consider that there is plenty of room for the development of fundamental research in the field of DESs because their compositional flexibility makes the number of DESs susceptible of preparation unlimited and so do the range of properties that DESs can attain. Ultimately, these properties can be transferred into the resulting materials in terms of both tailored morphologies and compositions. Thus, interesting applications can be easily envisaged, especially in those fields in which the preparation of high-tech products via low cost processes is critical. We hope that the preliminary work surveyed in this review will encourage scientists to explore the promising perspectives offered by DESs. PMID:22695767

Deep eutectic solvents (DES) resemble ionic liquids but are formed from an ionic mixture instead of being a single ionic compound. Here we present some results that demonstrate that surfactant sodium dodecyl sulfate (SDS) remains surface-active and shows self-assembly phenomena in the most commonly studied DES, choline chloride/urea. X-ray reflectivity (XRR) and small angle neutron scattering (SANS) suggest that the behavior is significantly different from that in water. Our SANS data supports our determination of the critical micelle concentration using surface-tension measurements and suggests that the micelles formed in DES do not have the same shape and size as those seen in water. Reflectivity measurements have also demonstrated that the surfactants remain surface-active below this concentration. PMID:26540438

The constitution of the quaternary system, Fe-Cr-Mn-C and to a lesser extent of the quinary system, Fe-Cr-Mn-Al-C were examined for in situ composite alloy candidates. Multivariant eutectic compositions were determined from phase equilibria studies wherein M7C3 carbides (approximately 30% by volume) formed from the melt within gamma iron. An extended field of the hexagonal carbide, (Cr, Fe, Mn)7 C3, was found without undergoing transformation to the orthorhombic structure. Increasing stability for this carbide was found for higher ratios of Cr/Fe(+) Cr + Mn. Aluminum additions promoted a ferritic matrix while manganese favored the desired gamma austenitic matrix. In coexistence with the matrix phase, chromium enters preferentially the carbide phase while manganese distributes equally between the gamma matrix and the M7C3 carbide. The composition and lattice parameters of the carbide and matrix phases were determined to establish their respective stabilities.

The development of high-temperature transport technologies for molten salt is a prerequisite and a key issue in the industrialization of pyro-reprocessing for advanced fuel cycle scenarios. The solution of a molten salt centrifugal pump was discarded because of the high corrosion power of a high temperature molten salt, so the suction pump solution was selected. An apparatus for salt transport experiments by suction was designed and tested using LiC-KCl eutectic salt. The experimental results of lab-scale molten salt transport by suction showed a 99.5% transport rate (ratio of transported salt to total salt) under a vacuum range of 100 mtorr - 10 torr at 500 Celsius degrees. The suction system has been integrated to the PRIDE (pyroprocessing integrated inactive demonstration) facility that is a demonstrator using non-irradiated materials (natural uranium and surrogate materials). The performance of the suction pump for the transport of molten salts has been confirmed.

Polonium-210 is an important radioactive product of neutron activation of molten lead-bismuth eutectic, a promising candidate coolant for advanced fast nuclear reactors. The radiological hazard potential associated with polonium can be significantly reduced by continuous online removal of polonium from the coolant. The removal method under investigation in this research is alkaline extraction. Chemical kinetic measurements were made to determine first and second order rate constants, activation energy, and heat of reaction at various temperatures using tellurium as a surrogate. First and second order alkaline extraction rate constants were measured to be: k1 = 10.05 e –52,274/RT and k2 = 167 e –97,224/RT. Alkaline extraction is dependent on temperature and was found to follow the Arrhenius rate law. The activation energy (Ea) ranged between 52,274 – 97,224 J mol-1. With a strong foundation of surrogate work completed, this work should be validated using polonium-210.

The dust waste formed during steelmaking in electric arc furnace (EAF) is rich in ferrous and nonferrous metals. Recycling of this dust as a raw material in iron or steel-making is hazardous and therefore it is mostly dumped. This paper demonstrates recycling of EAF dust through selective dissolution of metal oxides in a deep eutectic ionic liquid. It was found that about 60% of Zn and 39% of Pb could be dissolved from the dust when stirred for 48h in 1 choline chloride:2 urea ionic liquid at 60°C. The resultant electrolyte was subsequently fed to a conventional three-electrode cell where cyclic voltammetry (CV) measurements were conducted to describe its electrochemical behavior. Two deposition peaks were determined and ascribed to deposition of zinc and lead. Static potentials were successively applied to electrowin metallic zinc. SEM/EDX investigations showed that the zinc electrowon contained remarkable contents of lead. PMID:25156719

Deep Eutectic Solvents (DESs) have recently emerged as a new generation of ionic liquids for lignocellulose pretreatment. However, DESs contain salt components which tend to inactivate cellulase in the subsequent saccharification process. To alleviate this problem, it is necessary to evaluate the applicability of the DESs-Cellulase system. This was accomplished in the present study by first studying the stability of cellulase in the presence of selected DESs followed by applicability evaluation based on glucose production, energy consumption and kinetic performance. Results showed that the cellulase was able to retain more than 90% of its original activity in the presence of 10% (v/v) for glycerol based DES (GLY) and ethylene glycol based DES (EG). Furthermore, both DESs system exhibited higher glucose percentage enhancement and lower energy consumption as compared to diluted alkali system. Among the two DESs studied, EG showed comparatively better kinetic performance. PMID:25661309

Green Chemistry plays a more and more important role in implementing rules of sustainable development to prevent environmental pollution caused by technological processes, while simultaneously increasing the production yield. Ionic liquids (ILs) and deep eutectic solvents (DESs) constitute a very broad group of substances. Apart from many imperfections, ILs and DESs have been the most promising discoveries in the world of Green Chemistry in recent years. The main advantage of ILs is their unique physicochemical properties-they are very desirable from the technological point of view, but apart from these benefits, ILs appear to be highly toxic towards organisms from different trophic levels. DES areas of usage are very spread, because they cover organic synthesis, extraction processes, electrochemistry, enzymatic reactions and many others. Moreover, DESs seem to be a less toxic alternative to ionic liquids. New possibilities of applications and future development trends are sought and presented, including such important solutions of life branches as pharmaceuticals' production and medicine. PMID:26040266

Deep eutectic solvents (DES) can be formed by bioactive compounds or pharmaceutical ingredients. A therapeutic DES (THEDES) based on ibuprofen, a non-steroidal anti-inflammatory drug (NSAID), and menthol was synthesized and its thermal behavior was analyzed by differential scanning calorimetry (DSC). A controlled drug delivery system was developed by impregnating a starch:poly-ϵ-caprolactone polymeric blend (SPCL 30:70) with the menthol:ibuprofen THEDES in different ratios (10 and 20 wt%), after supercritical fluid sintering at 20 MPa and 50 °C. The morphological characterization of SPCL matrices impregnated with THEDES was performed by scanning electron microscopy (SEM) and micro-computed tomography (micro-CT). Drug release studies were carried out in a phosphate buffered saline. The results obtained provide important clues for the development of carriers for the sustainable delivery of bioactive compounds. PMID:26142248

Natural deep eutectic solvents (NADES) are a novel class of eutectics which show a unique potential as solubilizer of water insoluble compounds. The purpose of the current study was to evaluate the potential of NADES as a solvent for the hydrophobic photosensitizer curcumin for use in antimicrobial photodynamic therapy (aPDT). Two of the seventeen NADES initially prepared (i.e., NADES GS and MC3) solubilized >0.05mg/ml curcumin and were further characterized. The hydrolytic stability (i.e., t1/2) of curcumin in NADES was comparable to or up to 2-10 times higher than previously reported results in cyclodextrins and up to >1300 times higher than results reported in buffer at pH8. The photolytic stability increased by a factor 5.6-10 in GS compared to the most photostable cyclodextrin and surfactant preparations reported previously. This NADES seemed to lock curcumin in its colorless diketo conformer, resulting in higher photostability than in ethanol and in the NADES MC3. The curcumin-NADES preparations dissolved rapidly in aqueous media and formed supersaturated solutions of curcumin. Precipitation of curcumin was observed after ≤1h depending on the dilution factor (pH<8). The NADES MC3 containing curcumin photoinactivated Escherichia coli at a lower curcumin concentration (1.25μM) than in any previously investigated preparations of curcumin. The ability of NADES to lock curcumin within one specific molecular conformation and also to potentiate the phototoxic effect of this photosensitizer emphasizes the unique properties of the NADES as a solvent. PMID:26410725

The speciation of metals in solution controls their reactivity, and this is extremely pertinent in the area of metal salts dissolved in ionic liquids. In the current study, the speciation of 25 metal salts is investigated in four deep eutectic solvents (DESs) and five imidazolium-based ionic liquids using extended X-ray absorption fine structure. It is shown that in diol-based DESs M(I) ions form [MCl2](-) and [MCl3](2-) complexes, while all M(II) ions form [MCl4](2-) complexes, with the exception of Ni(II), which exhibits a very unusual coordination by glycol molecules. This was also found in the X-ray crystal structure of the compound [Ni(phen)2(eg)]Cl2·2eg (eg = ethylene glycol). In a urea-based DES, either pure chloro or chloro-oxo coordination is observed. In [C6mim][Cl] pure chloro complexation is also observed, but coordination numbers are smaller (typically 3), which can be explained by the long alkyl chain of the cation. In [C2mim][SCN] metal ions are entirely coordinated by thiocyanate, either through the N or the S atom, depending on the hardness of the metal ion according to the hard-soft acid-base principle. With weaker coordinating anions, mixed coordination between solvent and solute anions is observed. The effect of hydrate or added water on speciation is insignificant for the diol-based DESs and small in other liquids with intermediate or strong ligands. One of the main findings of this study is that, with respect to metal speciation, there is no fundamental difference between deep eutectic solvents and classic ionic liquids. PMID:24897923

Objective(s): Drug delivery through the skin can transfer therapeutic levels of drugs for pharmacological effects. Analgesics such as NSAIDs have gastrointestinal side effects and topical dosage forms of these drugs are mainly preferred, especially for local pains. Meloxicam is one of NSAIDs with no topical form in the market. In this research, we attempted to quantify the skin permeation of a meloxicam topical preparation and to show how permeation would be increased by using thymol as an enhancer. The effect of eutectic point of drug and thymol mixture on rate and extent of skin permeation was also studied. Materials and Methods: Different mixtures of thymol and meloxicam (2:8, 4:6, 5:5, 6:4, 8:2) were prepared and their melting point were obtained by differential scanning calorimetry. Then drug permeation was measured using diffusion cells and the Guinea pig skin. Results: Mixtures in ratios 5:5 and 4:6 of meloxicam / thymol showed a new endotherm at 149 and 140°C in DSC thermograms. The permeability of meloxicam from the creams containing 6:4, 5:5 and 4:6 ratios of meloxicam to thymol were 4.71, 15.2, 22.06 µg/cm2 respectively. This was significantly different from the cream of pure meloxicam (3.76 µg/cm2). Conclusion: This study set out to determine that thymol plays as a skin permeation enhancer and increases the meloxicam skin absorption and this enhancement is significant at the eutectic point of drug-enhancer mixture. PMID:24711894

Deep eutectic solvents (DESs) are basically molten salts that interact by forming hydrogen bonds between two added components at a ratio where eutectic point reaches a melting point lower than that of each individual component. Their remarkable physicochemical properties (similar to ionic liquids) with remarkable green properties, low cost and easy handling make them a growing interest in many fields of research. Therefore, the objective of pursuing this study is to analyze the potential of alcohol-based DES as an extraction medium for rotenone extraction from Derris elliptica roots. DES was prepared by a combination of choline chloride, ChCl and 1, 4-butanediol at a ratio of 1/5. The structure of elucidation of DES was analyzed using FTIR, {sup 1}H-NMR and {sup 13}C-NMR. Normal soaking extraction (NSE) method was carried out for 14 hours using seven different types of solvent systems of (1) acetone; (2) methanol; (3) acetonitrile; (4) DES; (5) DES + methanol; (6) DES + acetonitrile; and (7) [BMIM] OTf + acetone. Next, the yield of rotenone, % (w/w), and its concentration (mg/ml) in dried roots were quantitatively determined by means of RP-HPLC. The results showed that a binary solvent system of [BMIM] OTf + acetone and DES + acetonitrile was the best solvent system combination as compared to other solvent systems. It contributed to the highest rotenone content of 0.84 ± 0.05% (w/w) (1.09 ± 0.06 mg/ml) and 0.84 ± 0.02% (w/w) (1.03 ± 0.01 mg/ml) after 14 hours of exhaustive extraction time. In conclusion, a combination of the DES with a selective organic solvent has been proven to have a similar potential and efficiency as of ILs in extracting bioactive constituents in the phytochemical extraction process.

Deep eutectic solvents (DESs) are basically molten salts that interact by forming hydrogen bonds between two added components at a ratio where eutectic point reaches a melting point lower than that of each individual component. Their remarkable physicochemical properties (similar to ionic liquids) with remarkable green properties, low cost and easy handling make them a growing interest in many fields of research. Therefore, the objective of pursuing this study is to analyze the potential of alcohol-based DES as an extraction medium for rotenone extraction from Derris elliptica roots. DES was prepared by a combination of choline chloride, ChCl and 1, 4-butanediol at a ratio of 1/5. The structure of elucidation of DES was analyzed using FTIR, 1H-NMR and 13C-NMR. Normal soaking extraction (NSE) method was carried out for 14 hours using seven different types of solvent systems of (1) acetone; (2) methanol; (3) acetonitrile; (4) DES; (5) DES + methanol; (6) DES + acetonitrile; and (7) [BMIM] OTf + acetone. Next, the yield of rotenone, % (w/w), and its concentration (mg/ml) in dried roots were quantitatively determined by means of RP-HPLC. The results showed that a binary solvent system of [BMIM] OTf + acetone and DES + acetonitrile was the best solvent system combination as compared to other solvent systems. It contributed to the highest rotenone content of 0.84 ± 0.05% (w/w) (1.09 ± 0.06 mg/ml) and 0.84 ± 0.02% (w/w) (1.03 ± 0.01 mg/ml) after 14 hours of exhaustive extraction time. In conclusion, a combination of the DES with a selective organic solvent has been proven to have a similar potential and efficiency as of ILs in extracting bioactive constituents in the phytochemical extraction process.

With the tensile direction parallel to the fiber axis, the room temperature tensile data of the extruded pure aluminum and Al-Al{sub 3}Ni eutectic alloy with [111] fiber texture reveal strong texture hardening. The data of the extruded pure aluminum indicate low strain hardening rate and no Hall-Petch strengthening. In the initial stage of yielding in which the flow curves of the extruded pure aluminum and Al-Al{sub 3}Ni eutectic allow show a plateau-like flow behavior, primary slip is the major dislocation activity but it takes place in only limited subgrains. For the Al-Al{sub 3}Ni eutectic alloy, the presence of intragranular eutectic particles will diminish the texture hardening. In this situation, tangling of dislocations occurs in the early stage of yielding, and the plateau-like initial flow behavior no longer exists.